Deuterium Isotope Effects on (13)C-NMR Chemical Shifts of 10-Hydroxybenzo[h]quinolines

Deuterium isotope effects on (13)C-NMR chemical shifts are investigated in a series of 10-hydroxybenzo[h]quinolines (HBQ’s) The OH proton is deuteriated. The isotope effects on (13)C chemical shifts in these hydrogen bonded systems are rather unusual. The formal four-bond effects are found to be negative, indicating transmission via the hydrogen bond. In addition unusual long-range effects are seen. Structures, NMR chemical shifts and changes in nuclear shieldings upon deuteriation are calculated using DFT methods. Two-bond deuterium isotope effects on (13)C chemical shifts are correlated with calculated OH stretching frequencies. Isotope effects on chemical shifts are calculated for systems with OH exchanged by OD. Hydrogen bond potentials are discussed. New and more soluble nitro derivatives are synthesized.