Acceleration effect of poly(vinylpyrrolidone) on williamson reaction. II. Studies on the dissociation of sodium phenoxide in the presence of poly(vinylpyrrolidone)

In connection with the accelerating effect of poly(N‐vinylpyrrolidone) (PVP) on a Williamson reaction, PhONa + NC4H9Br → PhO‐(n‐C4H9) + NaBr, the ionic dissociation of sodium phenoxide (PhONa) was studied by means of conductance measurements and ultraviolet spectroscopy. Results suggest that the degree of dissociation of PhONa increased with the amount of PVP as well as N‐methylpyrrolidone (NMP), the monomeric analog, the effect of PVP being much larger than that of NMP at the same concentration. It is assumed that free phenolate anion produced by solvation of sodium cation with NMP or the pyrrolidone residues of PVP plays an important role in the acceleration of the reaction and that the higher reaction rates in PVP solution are due to the greater dissociation of PhONa.