Abiotic transformation of catechol and 1-naphthol in aqueous solution - Influence of environmental factors

The abiotic transformation of catechol and I-naphthol singly and in mixtures was tested in sterile Tris-HCl buffer with regard to several environmental factors including temperature (7 degreesC, 20 degreesC and 30 degreesC), lighting conditions, pH (between 7.0 and 9.5) and dissolved oxygen (at partial pressures of 0.0, 220, 2200, 11000 and 22000 Pa). Irrespective of lighting conditions, catechol autoxidation was confirmed in aerated medium with a rate independent of the presence of 1-naphthol but proportional to the dissolved oxygen concentration, to the pH (its half-disappearance occurred in 24 h at pH 8.5) and, to a lesser extent, to the incubating temperature (at 20 degreesC, 20% disappeared in 10 days at pH 7.0). Under alkaline conditions, the reaction of the anionic form (catecholate) with an equimolar concentration of molecular oxygen (O-2) led presumably to hydrogen peroxide anion (HO2-) and coloured polymerization products. When tested alone, 1-naphthol was not significantly influenced either by lighting conditions, incubating temperature or dissolved oxygen concentration. It was also found to be quite stable with respect to pH, with a 15-fold weaker transformation rate than for catechol at the highest pH used. When tested in a mixture with catechol, 1-naphthol was found to be involved in a new chemical oxidation reaction catalyzed by catecholate. The transformation of one mole of 1-naphthol consumes four moles of oxygen. In the presence of catechol, the stoichiometry of the I-naphthol transformation, under the influence of oxygen, suggests the possible formation of 2,5,6,8-tetrahydroxy 1,4-naphthoquinone via Lawsone (2-hydroxy 1,4-naphthoquinone) and naphthopurpurine (2,5,8-trihydroxy 1,4-naphthoquinone) as hypothetic intermediates. This is the first report of the autoxidation of 1-naphthol, catalyzed by catechol, in aqueous solution, in the absence of UV irradiation. (C) 2001 Elsevier Science Ltd. All rights reserved.