Strain energy modeling of simple and crowded aliphatic ketones: spectroscopic properties
Abstract Spectroscopic properties of ketones have been correlated with a structure-frequency micro-correlation made possible by dividing the ketone population into sub-populations, P i,i'. The structure and comportment of those ketones of the population that remain outside the correlations are treated in the discussion. The DARC/PELCO topological treatment is explained and demonstrated : it is based on the notion of ordered populations considered as hyperstructures or formal graphs. The correlations thus obtained, in IR, UV and 13 C NMR spectroscopy, are more exhaustive than those obtained with the above-mentioned micro-correlations, and their prediction potential, or “proference”, is very high. Variations in the geometry of compound structures resulting from an abundance of substitutions, as well as their relationship to conformational problems, are shown. A gempersubstituted β effect associated with a major strain release, leads to major deformations of angles and of interatomic distances.