STUDIES IN THE POLYOXYPHENOL SERIES: VIII. THE OXIDATION OF SUBSTANCES RELATED TO VANILLIN WITH SODIUM CHLORITE AND CHLORINE DIOXIDE

The research confirmed the fact that chlorine dioxide and sodium chlorite were not equivalent in their oxidizing properties. At 22 °C. or less, the oxidation of pyrogallol by aqueous sodium chlorite at pH 6 was very slow, but became very rapid on the acid side of pH 3.5. The amorphous, colored products probably did not include purpurogallin. Under similar circumstances p-hydroxybenzaldehyde was unaffected at pH 6; 22% was oxidized to p-benzoquinone (Dakin's reaction) at pH 5, and this amount increased to 39% at pH 1. The yield of benzoquinone was about 24% regardless of pH within the above range when aqueous chlorine dioxide was the oxidant. Sodium chlorite at pH 0.9 produced a 91% yield of methoxy-p-quinone from methoxy-p-hydroquinone; at pH 4 this product was mixed with 56% of 4,4′-dimethoxydiquinone, but near pH 6 a slower oxidation did not proceed beyond 4,4′-dimethoxyquinhydrone. Aqueous chlorine dioxide yielded at least 92% of monomeric methoxyquinone at all pH values between 1 and 6, probably in accord with the equation,[Formula: see text] The simultaneous formation of hydrogen peroxide was suspected, but not proved. In sharp distinction to the behavior of free phenols, veratraldehyde was not oxidized by aqueous chlorine dioxide between pH 6 and pH 3, but at pH 1 a slow reaction yielded up to 15% of veratric acid. Sodium chlorite produced about 92% of the same acid at pH 1 and pH 4, but its action was negligible at pH 5. Since by-product chlorine dioxide was ineffective at pH 4, it was possible to confirm the validity of the Jeanes–Isbell equation for the reduction of chlorous acid:[Formula: see text]The oxidation of acetylated vanillin was complicated by the occurrence of deacetylation. Red, chlorinated oils with quinoidal properties were also formed in most of the above oxidations.