Abstract
The structures and energies of axial and equatorial conformers and rotamers of 4-substituted tetrahydro-2H-thiopyran-1,1-dioxides (tetrahydrothiopyran-1,1-dioxides, thiacyclohexane-1,1-dioxides, thiane-1,1-dioxides, and 1,1-dioxothianes; CH3, CH2OH, CHO, COCH3, CN, F, Cl, Br, and OCOCH3) were calculated using the hybrid density functionals B3LYP, B3P86, and B3PW91, as well as MP2 and the 6-31G(d), 6-31G(2d), 6-31G(3d), 6-31G(d,p), and 6-31+G(d) basis sets. MP2/6-31+G(d)/ /HF/6-31+G(d) [−ΔG° = 1.73 kcal/mol], B3P86/6-31G(d) [−ΔG° = 1.75 kcal/mol], and B3PW91/6-31G(d) [−ΔG° = 1.85 kcal/mol] gave conformational free energy (ΔG°) values at 180 K for 4-methyltetrahydro-2H-thiopyran-1,1-dioxide which were similar to the reported experimental values for methylcyclohexane (−ΔG° = 1.80 kcal/mol), 4-methyltetrahydro-2H-thiopyran (−ΔG° = 1.80 kcal/mol), and other 4-methyl-substituted heterocycles. All levels of theory showed that the conformational preferences of the 4-methanoyl (4-formyl), 4-ethanoyl (4-acetyl), and 4-cyano substituents were small. The HF calculations gave conformational free energy (ΔG°) values for 4-chlorotetrahydro-2H-thiopyran-1,1dioxide which were closer to the experimental value than the MP2 and density functional methods. The best agreement with available experimental data for 4-bromotetrahydro-2H-thiopyran-1,1-dioxide was obtained from the HF/6-31G(2d), HF/6-31G(3d), and B3LYP/6-31G(2d) calculations, and, for 4-acetoxytetrahydro-2H-thiopyran-1,1-dioxide, from the HF/6–31G(3d) calculations. The conformational free energies (ΔG°) and relative energies (ΔE) of the conformers and rotamers have been compared with the correspondingly substituted cyclohexanes and tetrahydro-2H-thiopyrans and are discussed in terms of dipole–dipole (electrostatic) interactions and repulsive nonbonded interactions (steric) in the most stable axial and equatorial conformers. The axial S=O bond lengths are shorter than the equatorial S=O bond lengths and the C2–C3 bond lengths in the substituents with carbon-bonded to the ring are shorter than the C3–C4 and C4–C-5 bond lengths. In contrast, the C2–C3 bond lengths in the 4-halogen and 4-acetoxy substituents are longer than the C3–C4 and C4–C-5 bond lengths.
Similar content being viewed by others
REFERENCES
Eliel, E. L.; Wilen, S. H., Stereochemistry of Organic Compounds; Wiley: New York, 1994; Chapter 11.
Juaristi, E., Ed., Conformational Behavior of Six-Membered Rings; VCH: New York, 1995.
Bushweller, C. H., in Conformational Behavior of Six-Membered Rings; Juaristi, E., Ed.; VCH: New York, 1995; pp. 25-58.
Freeman, F.; Kasner, M. L.; Tsegai, Z. M.; Hehre, W. J., J. Chem. Ed. 2000, 77, 661.
Wiberg, K. B.; Hammer, J. D.; Castejon, H.; Bailey, W. F.; DeLeon, E. L.; Jarret, M., J. Org. Chem. 1999, 64, 2085.
Wiberg, K. B., J. Org. Chem. 1999, 64, 6387.
Winstein, S.; Holness, N. J., J. Amer. Chem. Soc. 1955, 77, 5562.
Freeman, F.; Kasner, M. L.; Hehre, W. J., J. Mol. Struct.(Theochem.) 1999, 487, 87.
Freeman, F.; Kasner, J. A.; Kasner, M. L.; Hehre, W. J., J. Mol. Struct.(Theochem.) 2000, 496, 19-39.
Freeman, F.; Phornvoranunt, A.; Hehre, W. J., J. Phys. Org. Chem. 1998, 11, 831.
Freeman, F.; Phornvoranunt, A.; Hehre, W. J., J. Phys. Org. Chem. 1999, 12, 176.
Freeman, F.; Phornvoranunt, A.; Hehre, W. J., J. Mol. Struct. (Theochem.) 1999, 492, 225.
Freeman, F.; Po, H. N.; Hehre, W. J., J. Mol. Struct.(Theochem.) 2000, 503, 145.
Freeman, F.; Asgari, N.; Hehre, W. J., J. Mol. Struct.(Theochem.), 2001, in press.
Freeman, F.; Gomarooni, F.; Hehre, W. J., J. Mol. Struct. (Theochem.) 2000, 535, 287.
Corey, E. J.; Feiner, N. F., J. Org. Chem. 1980, 45, 757.
Corey, E. J.; Feiner, N. F., J. Org. Chem. 1980, 45, 765.
Juaristi, E.; Cuevas, G., The Anomeric Effect; CRC Press: Boca Raton, FL, 1995; references therein.
Thatcher, G., Ed., The Anomeric Effect and Associated Stereoelectronic Effects; American Chemical Society Symposium Series 539; American Chemical Society: Washington, DC, 1993.
Kirby, A. J., The Anomeric Effect and Related Stereoelectronic Effects of Oxygen; Springer: Berlin, 1983.
Perrin, C. L., Tetrahedron 1995, 51, 11901.
Juaristi, E.; Cuevas, G.; Vela, A., J. Amer. Chem. Soc. 1994, 116, 5796; references therein.
Juaristi, E.; Cuevas, G., Tetrahedron 1992, 48, 5019; references therein.
Borsdorf, R.; Matzen, P. F.; Remane, H.; Zschunke, A., Z. Chem. 1971, 11, 21.
Remane, H.; Borsdorf, R.; Zschunke, A., Z. Chem. 1971, 11, 427.
Nagao, Y.; Goto, M.; Kida, K.; Shiro, M., Heterocycles 1995, 41, 419.
Wiberg, K. B.; Castejon, H.; Bailey, W. F.; Ochterski, J., J. Org. Chem. 2000, 65, 1181.
Foresman, J. B.; Frisch, A., Exploring Chemistry with Electronic Structure Methods, 2nd edn.; Gaussian, Inc., Pittsburgh, PA, 1996.
Alabugin, I. V., J. Org. Chem. 2000, 65, 3910; references therein.
Jonas, V.; Frenking, G., Chem. Phys. Lett. 1991, 127, 175.
Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Zakrzewski, V. G.; Montgomery, J. A.; Stratmann, R. E. Jr.; Burant, J. C.; Dapprich, S.; Millam, J. M.; Daniels, A. D.; Kudin, K. N.; Strain, M. C.; Farkas, O.; Tomasi, J.; Barone, V.; Cossi, M.; Cammi, R.; Mennucci, B.; Pomelli, C.; Adamo, C.; Clifford, S.; Ochterski, J.; Petersson, G. A.; Ayala, P. Y.; Cui, Q.; Morokuma, K.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Cioslowski, J.; Ortiz, J. V.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng, C. Y.; Nanayakkara, A.; Gonzalez, C.; Challacombe, M.; Gill, P. M. W.; Johnson, B.; Chen, W.; Wong, M. W.; Andres, J. L.; Gonzalez, C.; Head-Gordon, M.; Replogle, E. S.; and Pople, J. A., GAUSSIAN 98 (Revision A.6), Gaussian, Inc., Pittsburgh, PA, 1998.
Bondi, A., J. Phys. Chem. 1964, 68, 441.
Pauling, L., Nature of the Chemical Bond, 3rd edn.; Cornell University Press: Ithaca, NY, 1960; pp. 260-261.
Proserpio, D. M.; Hoffmann, R.; Levine, R. D., J. Amer. Chem. Soc. 1991, 113, 3217.
Chauvin, R., J. Phys. Chem. 1992, 96, 9194.
O'Keeffe, M.; Brese, N. E., J. Amer. Chem. Soc. 1991, 113, 3226.
Halgren, T., J. Amer. Chem. Soc. 1992, 114, 7827.
Allinger, N. L.; Zhou, X.; Bergsma, J., J. Mol. Struct.(Theochem.) 1994, 312, 69.
Carroll, F. A., Perspectives on Structure and Mechanism in Organic Chemistry; Brooks/Cole: New York, 1998; pp. 5-8.
Wiberg, K. B.; Murcko, M. A., J. Comput. Chem. 1987, 8, 1124.
Allinger, N. L.; Yuh, Y. H.; Lii, J.-J., J. Amer. Chem. Soc. 1989, 111, 8551.
Lowe, G.; Thatcher, R. J.; Turner, J. C. G.; Waller, A.; Watkin, D. J., J. Amer. Chem. Soc. 1988, 110, 8512.
Lambert, J. B.; Keske, R. G., J. Org. Chem. 1966, 31, 3429.
Eliel, E. L.; Chandrasenkaran, S., J. Org. Chem. 1982, 47, 4783.
Eliel, E. L.; Hargrave, K. D.; Pietrusiewicz, K. M.; Manoharan, M., J. Amer. Chem. Soc. 1982, 104, 3635.
Freeman, F.; Kasner, M. L.; Hehre, W. J., J. Mol. Struct.(Theochem.) 2001, 574, 19.
Freeman, F.; Hehre, W. J., J. Mol. Struct.(Theochem.) 2000, 529, 225.
Barbarella, G.; Dembech, P.; Garbesi, A.; Fava, A., Org. Magnetic Resonance 1976, 8, 469.
Willer, R. L.; Eliel, E. L., J. Amer. Chem. Soc. 1977, 99, 1925.
Barbarella, G.; Dembech, P.; Tugnoli, V., Org. Magnetic Resonance 1984, 22, 402.
Eliel, E. L.; Wilen, S. H., Stereochemistry of Organic Compounds; Wiley: New York, 1994; pp. 743-744.
Eliel, E. L.; Pietrusiewicz, K. M., Org. Magnetic Resonance 1980, 13, 193.
Eliel, E.; Pietrusiewicz, K. M., Polon. J. Chem. 1981, 55, 1265.
Freeman, F.; Nguyen, T.; Hehre, W. J., J. Mol. Struct.(Theochem.) 2001, 549, 203.
Kitching, W.; Olszowy, H.; Adcock, W., Org. Magnetic Resonance 1981, 15, 230.
Buchanan, G. W.; McCarville, A. R., Can. J. Chem. 1972, 50, 1965.
Buchanan, G. W., Can. J. Chem. 1982, 60, 2908.
Buchanan, G. W.; Preusser, S. H.; Webb, V. L., Can. J. Chem. 1984, 62, 1308.
Eliel, E. L.; Reese, M. C., J. Amer. Chem. Soc. 1968, 90, 1560.
Jensen, F. R.; Bushweller, C. H.; Beck, B. H., J. Amer. Chem. Soc. 1969, 91, 344.
Hofner, D.; Lesko, S. A.; Binsch, G., Org. Magnetic Resonance 1978, 11, 179.
Schneider, H.-J.; Hoppen, V., J. Org. Chem. 1978, 43, 3866.
Bugay, D. D.; Bushweller, C. H.; Danehy, C. T.; Hoogasian, S.; Blersch, J. A.; Leenstra, W. R. J. H., J. Phys. Chem. 1989, 93, 3908.
Chu, P.-S.; True, N. S., J. Phys. Chem. 1985, 89, 5613.
Salzner, U.; Schleyer, P. v. R., J. Org. Chem. 1994, 59, 2138.
Cremer, D.; Binkley, J. S.; Pople, J. A., J. Amer. Chem. Soc. 1976, 98, 6836.
Shen, Q.; Peloquim, J. N., Acta Chem. Scand. 1988, 42, 367.
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Freeman, F., Gomarooni, F. & Hehre, W.J. An Ab Initio Molecular Orbital Theory and Density Functional Theory (DFT) Study of Conformers and Rotamers of 4-Substituted (Methyl, Hydroxymethyl, Methanoyl, Ethanoyl, Cyano, Fluoro, Chloro, Bromo, Acetoxy) Tetrahydro-2H-thiopyran-1,1-dioxides. Structural Chemistry 13, 115–131 (2002). https://doi.org/10.1023/A:1015700414427
Issue Date:
DOI: https://doi.org/10.1023/A:1015700414427