Iron polyphthalocyanine

Butyroin has been prepared by reductive condensation of ethyl butyrate with sodium in xylene, or with sodium in the presence of chloro-trimethylsilane. and by reduction of 4,5-octanedlone with sodium l-benzyl-3-carbamoyl-l,4-dihydropyridine-4-sulfinate in the presence of magnesium chloride or with thiophenol in the presence of iron polyphthalocyanine as electron transfer agent.This acyloin has also been obtained by oxidation of (E)-4-octene with potassium permanganate and by reaction of... 

Organic Catalysts. III. The Catalytic Action of Copper-Iron Polyphthalocyanine... 

Copper-iron-polyphthalocyanine [251,252] showed a specific catalysis for the oxidations of saturated aldehydes and substituted benzaldehydes with oxygen. The catalytic reaction was solvent dependent so that tetrahydrofuran, ethanol, acetonitrile, ethyl acetate and anisole inhibited benzaldehyde oxidation while oxidation occurred readily in benzene or acetone. Benzaldehyde was catalytically oxidized with copper-iron-polyphthalocyanine and oxygen to give a quantitative yield of a mixture of perbenzoic (61%) and benzoic (39%) acids. Reaction was carried out at 30 °C and atmospheric pressure of oxygen and exhibited no induction period. By contrast p-methyl and p-chlorobenzaldehyde had induction periods of 8 and 15 min respectively while no oxidation of p-substituted benzaldehydes was observed when the para-substituent was NO2, OH, OCH3, or N(CH3)2. 

Inoue, Kida and Imoto [252] found that the oxidation of unsaturated aldehydes such as cinnamaldehyde and acrolein proceeded much more slowly than did oxidation of the saturated substrates in the presence of copper-iron-polyphthalocyanine. As in the case of the saturated acids the products were a mixture of the peracid and the corresponding carboxylic acid. Other groups have recently investigated the oxidation of unsaturated aldehydes in the presence of metal complexes [253-260]. Methacrylic acid and acetic acid were formed in the copper naphthenate catalyzed oxidation of methacrolein [255]. The oxidation of acrolein to acrylic acid was catalyzed by Co, Ni, Mn and Cu acetates [256]. It was found that at concentrations of acrolein in... 

Zhang R, Peng Y, Li Z, Li K, Ma J, Liao Y, Zheng L, Zuo X, Xia D (2014) Oxygen electroreduction on heat-treated multi-walled carbon nanotubes supported iron polyphthalocyanine in acid media. Electrochim Acta 147 343-351... 

A small number of papers that cover mechanistic aspects deal with the factors that stabilize the developing carbonium ion in the hydrolysis of 0,S-thioacetaIs. An electron-transfer, mild reduction system (iron polyphthalocyanine) has been shown to reduce benzil dithioacetal to the / -keto-sulphide [PhCOCPh(SPh)2 PhCOCHPhSPh]. Homolysis of dithioacetals on heating with BuKDOBu in PhCI followed by a 1,2-shift of an alkylthio-group leads to l,2-bis-(alkylthio)alkyl compounds/ ... 

The potent reductant Smh readily reduces a-alkylthio, a-sulfinyl and a-sulfonyl ketones at -78 °C A mixture of iron(II) polyphthalocyanine and thiophenol has been used to reduce a-halo, a-alkylthio, and a,a-bis(alkylthio) ketones. The iron compound apparently reacts as an electron transfer mediator the actual source of electrons is the thiophenol, which is converted to diphenyl disulfide in the course of the reaction. 

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