Applications of nuclear magnetic resonance spectroscopy to the study of medium-sized rings. I. Conformational properties of cycloheptane. II. Conformational properties of cycloöctane

• Main Author: Glazer, Edward Stanley
• Format: Others
• Published: 1966
• Online Access: https://thesis.library.caltech.edu/9175/1/Glazer_es_1966.pdf; Glazer, Edward Stanley (1966) Applications of nuclear magnetic resonance spectroscopy to the study of medium-sized rings. I. Conformational properties of cycloheptane. II. Conformational properties of cycloöctane. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/3V4M-PW36. https://resolver.caltech.edu/CaltechTHESIS:09242015-150926803 <https://resolver.caltech.edu/CaltechTHESIS:09242015-150926803>

<p>Conformational equilibrium in medium-sized rings has been investigated by the temperature variation of the fluorine-19 n.m.r. spectra of 1, 1-difluorocycloalkanes and various substituted derivatives of them. Inversion has been found to be fast on the n.m.r. time scale at -180˚ for 1, 1-difluorocycloheptane, but slow for 1, 1-difluoro-4, 4-dimethylcycloheptane at -150˚. At low temperature, the latter compound affords a single AB pattern with a chemical-shift difference of 841 cps. which has been interpreted in terms of the twist-chair conformation with the methyl groups on the axis position and the fluorine atoms in the 4-position. At room temperature, the n.m.r. spectrum of 1, 1-difluoro-4-<u>t</u>-butylcycloheptane affords an AB pattern with a chemical-shift difference of 185 cps. The presence of distinct <u>trans</u> and <u>gauche</u> couplings from the adjacent hydrogens has been interpreted to suggest the existence of a single predominant form, the twist chair with the fluorine atoms on the axis position.</p> <p>Investigation of 1, 1-difluorocycloöctane and 1, 1, 4, 4-tetrafluorocycloöctane has led to the detection of two kinetic processes both having activation energies of 8-10 kcal./mole but quite different A values. In light of these results eleven different conformations of cycloöctane along with a detailed description of the ways in which they may be interconverted are discussed. An interpretation involving the twist-boat conformation rapidly equilibrating through the saddle and the parallel-boat forms at room temperature is compatible with the results. </p>