ALICYCLIC KETYLS: II. TEMPERATURE DEPENDENCE OF THE CONFORMATIONAL MOBILITY OF MEDIUM-SIZED RINGS

The electron paramagnetic resonance spectra of ketyls derived from alicyclic ketones containing from 6 to 12 carbons have been recorded in 1,2-dimethoxyethane or dimethoxymethane at temperatures from −96 to +87 °C. At −96° individual conformers of the cyclohexyl ketyl are observed with hyperfine couplings in close agreement with that of the conformationally 'frozen' 4-tert-butyl analogue at room temperature. The cycloheptyl ketyl conformational equilibrium between forms which have a plane of symmetry through the C—O bond axis is 'frozen' with respect to the spectrometer frequency at temperatures from −40 to +88 °C. Cyclooctyl ketyl equilibrates at ordinary temperatures between two conformers lacking a plane of symmetry through the C—O bond axis. The electron paramagnetic resonance spectra of the ketyls derived from 10- and 12-membered rings show dramatic temperature dependence, which is interpreted in terms of two or more simultaneous conformational equilibria. Values for the dihedral angles of the alpha protons and for the spin density on the sp2 carbon are derived.