31P NMR Spectroscopy in Wood Chemistry. I. Model Compounds

The quantitative reaction in an NMR tube of 1,3,2-dioxaphospholanyl chloride (I) with compounds bearing active hydrogens was explored as a simple method for derivatizing the labile centres known to occur in lignins. Derivatives of phenols, alcohols and carboxylic acids with (I) gave ³¹P chemical shifts which appeared in different ranges of the NMR spectra. Any ortho substitution onto the aromatic ring of phenols significantly affected the magnitude of the ³¹P NMR chemical shifts, while para and/or meta substituents had a much smaller effect. A clear distinction between guaiacyl, syringyl and unsubstituted phenolic hydroxyls can thus be made in mixtures of model compounds. Primary alcohols were clearly distinguished from secondary and tertiary alcohols in their derivatives with (I), while different ³¹P NMR signals for derivatives of erythro and threo forms of lignin-like model compounds were identified. While alcohols, phenols and simple carboxylic acids on reaction with (I) gave derivatives that were substitution products, aldehydes reacted via a distinctly different addition mechanism; ketones did not react at all.