Kinetic studies on the reactions of electrogenerated 9,10-diphenylanthracene cation radical with water and alcohols by means of column-electrolytic stopped-flow method.

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The reactions of 9,10-diphenylanthracene cation radical (DPA+·) with water and alcohols in acetonitrile (AN) were studied using a novel column-electrolytic stopped-flow spectrophotometric method. The reaction was first-order with respect to DPA+· in all reactions. The reaction orders of other reactants were determined by plotting the logarithms of the apparent first-order rate constants (kapp's) against the logarithms of the concentration of reactants. The plot of logkapp vs. log [alcohols] was linear, and hence the reaction was clearly determined to be second-order. On the other hand, the logkapp vs. log [water] plot did not show a linear relationship. Similar results were obtained in the reactions of 9,10-dimethylanthracene cation radical with water and methanol. Comparing the results obtained with water and alcohols, and considering the changes in the physicochemical properties of the AN–water medium, it was concluded that the reaction of water was second-order, though it had been believed previously to be first-order. Products of the reactions are trans- and cis-9,10-dialkoxy-9,10-diphenyl-9,10-dihydroanthracene in many cases.
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