Carbon-13 n.m.r. studies. Part 66—13C spectra of several methyl,hydroxymethyl and carboxylic acid derivatives of bicyclo[2.2.1]heptane and bicyclo[2.2.2]octane

The ¹³C n.m.r. spectra of a series of 52 substituted norbornanes, norbornenes, bicyclo[2.2.2]octanes and -octenes have been recorded to examine the stereochemical effects of closely neighboring substituents on the carbon shieldings of these well-defined molecular frameworks. These moderately rigid skeletons permit detailed examination of a variety of orientations of substituents and, in this study, attention has been focused on a series of vicinally substituted systems. The substituents include methyl, hydroxymethyl and carboxylic acid groups for comparison with earlier data for several bicyclic alcohols and hydrocarbons, from which conclusions regarding the conformational preferences of the hydroxyl group may be drawn. The deviations of the observed shieldings from those predicted by simple additivity follow definite patterns which should be useful for stereochemical assignments in related systems.