Methoxy 13C NMR Chemical Shift as a Molecular Descriptor in the Structural Analysis of Flavonoids and Other Phenolic Compounds

Abstract

The interpretation of nuclear magnetic resonance (NMR) chemical shifts plays an increasingly important role in the structure elucidation of flavonoids. Despite the fact that the 3H signal of the methoxy (OMe) group appears as a singlet in the 1H NMR spectrum, its chemical shift is not reliably indicative of the OMe-substitution in the aromatic rings, unlike its 13C NMR chemical shift, which can be useful for the determination of the molecular structure of flavonoids. For example, the chemical shift of ortho-substitutions is at 56 ± 1 ppm for flavonoids having one OMe-substituent in either the ortho or orthó position and 61.5 ± 2 ppm for those having substituents in both ortho positions. The nuclear Overhauser effect spectroscopy ( δH-OMe→ ortho-aryl-H or adjacent substituent) and heteronuclear multiple-bond correlation ( δH-OMe→ ipso-aryl-C) data have been widely employed for the structure analysis of flavonoids and to identify the site of OMe-substitution. Thus, OMe chemical shifts can act as molecular descriptors. However, we have noticed that there are several examples that are not in accordance with this generalization, and a reinvestigation of such reported data seems to be relevant for reconsideration of assigned structures, and a few examples are cited herein.