Electrochemical oxidation of 5-hydroxytryptophol. I: Studies in acid solution

The oxidation chemistry of the endogenous central nervous system indole 5-hydroxytryptophol (5-HTOL) has been studied at pH 2 using electrochemical methods. The first voltammetric oxidation peak (I) appears to involve an initial one-electron abstraction giving a transient radical cation that, in the rate-controlling step, deprotonates to give a neutral radical. A radical-substrate reaction then occurs to give a dimer radical which is further oxidized to yield three simple dimers (4,4'-,4,6'-, and 2,4'-linked). The neutral radical can be further oxidized (1e) to a quinone imine that, as a result of very fast follow-up chemistry and electrochemistry, yields tryptophol-4,5-dione (B) which has been isolated in pure form. Reactions between intermediate species also result in three dimers containing residues of 5-HTOL and B and an unusual oxygen-bridged trimer.