Homogeneous oxidation of aromatics in nucleus with peracetic acid catalyzed by iron and manganese phthalocyanine complexes

Naphthalene Oxidation by Peracetic Acid Catalysed by Mn(III) Porphine-like Complexes: Nature of Intermediates and Pathways of their Formation

“…CH 3 CN of HPLC grade was used after additional purification by boiling and distillation with potassium permanganate. Solutions of peracetic acid in acetic acid (1.3-1.9 M) were prepared as described in Refs [5] and [6].…”

“…Previously [5,6] we established that in the ONPcMnCl-catalysed reaction the products of oxidation of naphthalene (Nf) and its methyl derivatives by AcOOH in CH 3 CN were the corresponding 1,4-naphthoquinones (maximal yields [19] up to 60% for 2,3-dimethylNf). Quinone yield values determined at the end of the reaction ('initial' yield Z Q in = 10% for Nf) were found to be 1.5-5 times lower than after heating the neutralized reaction mixture (maximal yield Z Q max = 52% for Nf).…”

“…For instance, mono-oxygenation properties of cytochrome P-450 have been demonstrated in naphthalene hydroxylation to 1-naphthol via intermediate 1,2-epoxy-1,2-dihydronaphthalene formation [3]. However, there are few data on model systems with porphyrins and porphine-like complexes [4][5][6][7] and non-porphinoid metal complexes [8][9][10][11] as catalysts of non-activated aromatic oxidation in the nucleus. In previous reports [5,6] we described the oxidation of naphthalene (Nf) and its methyl derivatives (2-methyl-and 2,3-dimethylNf) by peracetic acid (AcOOH) in acetonitrile in the presence of Fe(II) and Mn(III) 3,5-octanitropthtalocyanine (ONPcM).…”

“…Thus we were interested in studying the reactivity of Mn oxene complexes in aromatic oxidation to see whether they are the only species which can transfer an oxygen atom (or atoms) from AcOOH to an aromatic molecule. The simple method of AcOOH preparation from 30% H 2 O 2 and acetic anhydride described previously [5,6] and the homogeneous conditions of this reaction facilitate both the preparative application and a mechanistic study.…”

“…However, there are few data on model systems with porphyrins and porphine-like complexes [4][5][6][7] and non-porphinoid metal complexes [8][9][10][11] as catalysts of non-activated aromatic oxidation in the nucleus. In previous reports [5,6] we described the oxidation of naphthalene (Nf) and its methyl derivatives (2-methyl-and 2,3-dimethylNf) by peracetic acid (AcOOH) in acetonitrile in the presence of Fe(II) and Mn(III) 3,5-octanitropthtalocyanine (ONPcM). More recently [7] it has been found that Fe(III)-and Mn(III)-containing metalloporphyrins catalyse the oxidation of 2-methylnaphthalene by potassium monopersulfate to a mixture of two naphthoquinones, 2-methyl-1,4-naphthoquinone and 6-methyl-1,4-naphthoquinone, in yields up to 97%.…”