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Abstract: Oxidation of 5×10-3M noradrenaline in aqueous phosphate buffer, pH 7.4, with K3Fe(CN)6, NaIO4 or Fe2+/EDTA/H2O2 followed by extraction with ethyl acetate and acetylation with Ac2O/Pyr led to a main reaction product which was isolated and identified as 4-[bis-(1H-5,6-diacetoxyindol-2-yl)methyl]-1,2-diacetoxybenzene, an unprecedented [bis-(indol-2-yl)methyl]-benzene derivative unsubstituted on the 3-position of the indole rings. This product was also obtained in 40% yield by reaction of 5,6-dihydroxyindole with 3,4-dihydroxybenzaldehyde. Other components of the oxidation mixture were 1-acetyl-3,5,6-triacetoxyindole, derived from noradrenolutin, and 5,6-diacetoxyindole, originating from cyclisation/dehydration of the o-quinone of noradrenaline, along with some 3,4-diacetoxybenzaldehyde. Inspection of the aqueous phase revealed the presence of 3,4-dihydroxymandelic acid and 3,4-dihydroxybenzaldehyde, derived from oxidative breakdown of the 2-amino-1-hydroxyethyl chain via a p-quinomethane intermediate. These results disclose new aspects of the oxidative chemistry of noradrenaline beyond the aminochrome stage and provide a route to novel [bis-(indol-2-yl)methyl]-benzene derivatives of potential pharmacological interest. [Copyright &y& Elsevier]

In the presence of excess H2O2, oxidation of dopamine was diverted from the usual pigment-forming pathway to afford 6-hydroxydopamine and then a colorless reaction mixture comprising a polar non-extractable product. The latter was obtained in 20% yield by oxidation of 6-hydroxydopamine and was tentatively formulated as the novel 5-(2-aminoethyl)-2-hydroxy-5-(3-hydroxy-2-oxotetrahydro-1aH-oxireno[2,3]cyclopenta[1,2-b]pyrrol-3a(4H)-yl)cyclohex-2-ene-1,4-dione by extensive spectral analysis and conversion to a tetraacetyl derivative. Mechanistic experiments suggested that formation of the product proceeds via 6-hydroxydopamine by H2O2-dependent epoxidation and cyclization steps followed by dimerization and ring contraction with decarboxylation. [Copyright &y& Elsevier]

Abstract: An unusual rearranged trimer, 2-(2-amino-4,5-dihydroxybenzyl)-6,7-dihydroxy-3-(5,6-dihydroxyindol-3-yl)quinoline (1a), was obtained as the acetyl derivative (1b) by mild acid-promoted polymerization of 5,6-dihydroxyindole at pH 2. Compound 1b proved to be a selective fluoride-sensing compound, transducing F− binding into a distinct absorption at 414nm and a marked fluorescence enhancement at 489nm. [Copyright &y& Elsevier]