Conformational analysis and steric effects of substituents in derivatives of 3-oxo-, 3-imino-, and 3-methylenecyclohexene |
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Authors: | O V Shishkin E V Solomovich M Yu Antipin A S Petrenko L A Kutulya |
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Institution: | (1) A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 ul. Vavilova, 117813 Moscow, Russian Federation;(2) Institute of Single Crystals, National Academy of Sciences of Ukraine, 60 prosp. Lenina, 310001 Kharkov, Ukraine |
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Abstract: | The equilibrium conformations and the inversion barriers of the rings in 3-oxo-, 3-imino-, 3-methylenecyclohexenes and in
their methyl,tert-butyl, and phenyl derivatives were calculated by molecular mechanics. The unsubstituted molecules adopt a sofa conformation.
The nonbonded interactions between substituents at positions 2 and 4 and the exocyclic double bond lead to a change in the
conformation of the ring to a half-chair. The effect is enhanced as the volume of the substituent increases in the series
of the oxo, imino, and methylene derivatives. Substituents at other positions of the ring affect only slightly the equilibrium
conformation. The results of calculations were confirmed by X-ray structural analysis of 2-(4-benzoyloxybenzyl)-6-isopropyl-3-methylcyclohex-2-enone.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1995–2000, November, 1997. |
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Keywords: | 3-oxo- 3-imino- and 3-methylenecyclohexenes conformational analysis X-ray structural analysis molecular mechanics |
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