Oxydation selective dans l'ethyleneglycol de l'anthracene en anthraquinone par O2, Catalysee par CuBr2

Catalyzed oxidation kinetics of anthracene with oxygen in ethylene glycol

“…The final reaction product is anthraquinone (AQ) and the intermediate is 9-oxo-9,10-dehydroanthracene-10-0888-5885/87/2626-2401$01.50/0 spiro-2-dioxalane (I) (Scheme I, eq 9) as we have identified by IR and RMN and which has also been described by Brossard et al (1977). No other products were detected.…”

“…No kinetic data are available in the literature, but we have results (Brossard et al, 1977; Muller and Bobillier, 1981; Koshitani et al, 1982) of the yield at certain temperatures and times of the reaction for anthracene oxidation in several solvents (dioxane, benzene/TBHP, ethylene glycol, diglyme) and catalysts (Br2Cu(OX), RhCl(PPh3), RhCO(PPh3)3Mo(CO)6). From these data, we have calculated in an approximate way the first-order rate constants.…”

“…Studies of this oxidation have been carried out in the gas phase with several catalysts, e.g., with vanadium (Ghosh and Nair, 1980; Sen et al, 1979). The possible economic advantages of mild conditions and lower temperatures working in the liquid-phase catalyst have promoted different studies and processes, as with chromates (Henglein, 1963;Weissermel and Arpe, 1978), with nitric acid (Kumar and Sekhar, 1982), and with metallic salt catalysts Ce(IV) (Rindone and Scolastico, 1971), Cu(II) (Brossard et al, 1977;Koshitani et al, 1982), or metallic complexes (Muller and Bobillier, 1981).…”

“…Some metals like copper seem to be good catalysts in the liquid phase, but there are no practical studies on these reactions. Brossard et al (1977) identified an intermediate of the reaction but gave little experimental data and made no kinetic study. In this paper, we study the Br2Cu-catalyzed oxidation of anthracene by air and ethylene glycol as a solvent, to clarify the nature and regime of the reaction from the kinetic data of the overall process, and on this basis we propose a mechanism of the reaction.…”

Oxidation kinetics of anthracene with nitrogen dioxide in acetic acid

“…Due to the advantages involved in carrying out anthracene oxidation at low temperature and under generally moderate conditions, various systems in the liquid phase have been studied. Thus, proposals have been made for the use of oxidants such as oxygen and/or nitric acid (Olivier and Gothlich, 1968; Das and Das, 1982); ammonium dichromate Bobillier, 1983 and1985); cerium (IV) ammonium nitrate (Rindone and Scolastico, 1973; Mittal, 1983 and1985); oxygen in the presence of copper (11) bromide (Brossard et al, 1977;Cepeda y Diaz, 1987), tertbutylhydroperoxide (Muller and Bobillier, 198 1 and 1985) or copper (11) chloro complexes (Koshitani et al, 1982); potassium bromate (Banerjee et al, 1983); and ammonium persulfate catalyzed by cerium ammonium nitrate, silver nitrate, and sodium dodecyl sulfate (Skarzewski, 1984).…”