Ml. Andersen et Ddm. Wayner, Electrochemistry of electron transfer probes. alpha-aryloxyacetoveratronesand implications for the mechanism of photo-yellowing of pulp, ACT CHEM SC, 53(10), 1999, pp. 830-836
Standard potentials (E degrees) of a series of substituted alpha-aryloxyace
toveratrone derivatives have been determined from a correlation of the C-13
NMR chemical shifts of the carbonyl group and a similar correlation (E deg
rees vs. C-13 NMR shifts) within a series of alpha-anilinoacetoveratrones.
Using these potentials the rate constants for fragmentation of the radical
anions were determined by digital simulation of the voltammetric waves. The
rate contants for C-O cleavage in the radical anions correlate with the pK
(a) of the corresponding phenols. The fragmentations are all in the activat
ed region of a general free energy relationship for this class of compound
(alpha=0.5). The standard potential and rate constant for fragmention of th
e alpha-guaiacoxyacetoveratrone radical anion also were determined. This sp
ecies is a model compound for one of the lignin substructures. The implicat
ion of these results on the currently accepted mechanism for photoyellowing
of lignin rich paper is discussed.