Oxidation of 3,4-dihydroxybenzyl alcohol: a sclerotizing precursor for cockroach ootheca.

The oxidation of 3,4-dihydroxybenzyl alcohol, one of the sclerotizing precursors for the tanning of the ootheca of cockroach Periplaneta americana, is reported for the first time. Mushroom tyrosinase catalyzed oxidation of 3,4-dihydroxybenzyl alcohol generated the corresponding quinone which was found to be unstable and readily transformed to produce 3,4-dihydroxybenzaldehyde as the stable product probably through the intermediary formation of a quinone methide. Phenoloxidase isolated from the left collateral gland of P. americana also catalyzed this new reaction. When the enzymatic oxidation of 3,4-dihydroxybenzyl alcohol was performed in the presence of a test protein such as lysozyme, the reactive species formed, caused the oligomerization of test protein. Similar studies with collateral gland proteins, failed to generate oligomers, but produced insoluble polymeric proteins. The probable fate of 3,4-dihydroxybenzyl alcohol for the tanning of cockroach ootheca is discussed.