Beschreibung:
<jats:title>Abstract</jats:title><jats:p>Conformationally rigid systems such as xylopyranose 1,2,4‐ortho esters (<jats:bold>1a</jats:bold>) and (<jats:bold>1b</jats:bold>) and 10‐methoxy‐6‐aza‐isoadamantane (<jats:bold>2</jats:bold>), for which the identity of conformations both in the crystalline state and in solution can reasonably be assumed, provide good models for the study of experimental correlations between the spin–spin coupling constants (<jats:italic>J</jats:italic>) of the vicinal protons and the dihedral bond angles (DBA) determined from an X‐ray study in the HCCH bond system. The Karplus equations and their modifications (with and without corrections for the electronegativity of adjacent groups) were found to be unable to provide satisfactory correlations between these parameters. Optimum coefficients for the equations connecting the <jats:italic>J</jats:italic> and DBA values with corrections for electronegativity were calculated by the least squares method. The same procedure was used to obtain an equation connecting the <jats:italic>J</jats:italic> with DBA values using the sum of the chemical shifts as a measure of the electronic factors affecting the <jats:italic>J</jats:italic> ∝ DBA dependence. The accuracy of the equation thus obtained lies within ±18% as opposed to ±48% for the original Karplus equations. A similar correlation was obtained for the angles between the intercrossing lines formed by the directions of the vicinal CH bonds (ILA). When combined with the sum of chemical shifts, ILA provides a better correlation with the coupling constants <jats:italic>J</jats:italic> than the conventional parameter DBA.</jats:p>