Pairwise effects of chlorine substituents on the 13C NMR chemical shifts of dichlorobicyclo[2.2.1]heptanes (norbornanes)

The ¹³C NMR spectra of nine dichlorinated bicyclo[2.2.1]heptanes (norbornanes) have been measured and assigned. The pairwise effects of chlorine substituents which cause deviations from the additivity of single-substituent effects were investigated and are discussed. The largest effect found is the high-field shift of carbons bearing vicinal cis substituents. In the case of geminal substitution deviations from additivity were found to be to low field and large in the γ, smaller in the β and negligible in the α chemical shifts. The observed deviations for 1,3-disubstituted cases vary from ?3.2 to +1.1 ppm at different carbons, allowing no simple explanation. Replacement of α-hydrogen in a diaxial 1,3-arrangement by CH₃, OH or CI causes the single substituent effect, namely the γ_a effect, to change considerably.