High resolution C nuclear magnetic resonance spectra for symmetrical orthodihalobenzenes including long-range CH couplings

Analysis of high resolution ¹³C NMR spectra for symmetrical orthodihalobenzenes have provided all long-range ¹³CH coupling values in orthodichloro-, dibromo-, and diiodobenzene. Furthermore, since the analyses were sensitive to the sign of the coupling constants, the relative signs of these long-range ¹³CH couplings have been determined from unique spectral fits. The substituent effects on the chemical shifts in this series of compounds appear to be additive. The ¹³CH couplings are compared with coupling values in other compounds and are shown to be related to substituent electronegativity. The absolute magnitude of the ¹³CH couplings for these halogen-substituted compounds are larger than those observed in benzene, with but one exception. In all cases, three-bonded ¹³CH couplings are found to be larger than the two-bond values.