Iron tetrasulfophthalocyanine

We have developed an efficient and practical method for clean oxidation of starch (21-23) resulting in the oxidation of primary alcohol function in Ce position and the cleavage of vicinal diols in C2 and C3 position (Figure 30.2). We used small amounts of cheap iron tetrasulfophthalocyanine catalyst, pure water as reaction medium and H2O2 as clean oxidant to achieve a one-pot conversion of starch resulting in the introduction of aldehyde and carboxyl functions in polymer chains. The iron content... 

The heterogeneous catalytic system iron phthalocyanine (7) immobilized on silica and tert-butyl hydroperoxide, TBHP, has been proposed for allylic oxidation reactions (10). This catalytic system has shown good activity in the oxidation of 2,3,6-trimethylphenol for the production of 1,4-trimethylbenzoquinone (yield > 80%), a vitamin E precursor (11), and in the oxidation of alkynes and propargylic alcohols to a,p-acetylenic ketones (yields > 60%) (12). A 43% yield of 2-cyclohexen-l-one was obtained (10) over the p-oxo dimeric form of iron tetrasulfophthalocyanine (7a) immobilized on silica using TBHP as oxidant and CH3CN as solvent however, the catalyst deactivated under reaction conditions. 

The water-soluble iron tetrasulfophthalocyanine (FePcS) complex, which is cheap and available on an industrial scale, was also a very active and selective catalyst for the oxidation reaction. Starches of different origin (potatoes, rice, wheat, com) were oxidized by H202 following two operating modes, viz. oxidation in aqueous suspension and oxidation by incipient wetness. 

Chlorinated aromatic compounds such as 2,4,6-trichlorophenol (278) are well known recalcitrant pollutants because of their slow biodegradation by microorganisms. Hydrogen peroxide oxidation of (U- C)-278 catalyzed by FePcS (iron tetrasulfophthalocyanine) was... 

Recently, controlled procedures for the covalent anchoring of iron tetrasul-fophthalocyanine onto amino-modified silicas have been developed to fix the complex either in a monomer or dimer form.80 Remarkably, the normally inactive dimeric oxo iron tetrasulfophthalocyanine is an active and selective... 

Gao X, Wang J, Ma Z, Ye J (2014) Iron tetrasulfophthalocyanine functionalized graphene nanosheets foroxygen reduction reaction in alkaline media. Electrochim Acta 130 543-550... 

Beyrhouty, M., Sorokin, A., Daniele, S., et al. (2005). Combination of Two Catalytic Sites in a Novel NanocrystaUine Ti02-iron Tetrasulfophthalocyanine Material Provides Better Catalytic Properties, New J. Chem., 29, pp. 1245-1248. 

Fashedemi OO, Ozoemena KI (2011) A facile approach to the synthesis of hydrophobic iron tetrasulfophthalocyanine (FeTSPc) nano-aggregates on multi-walled carbon nanotubes a potential electrocatalyst for the detection of dopamine. Sens Acmators B 160 7-16... 

Fig. 8.2 The decomposition of H2O2 with or without catalyst at 52°C and pH 8.4. (From P. Tolvanen, A. Sorokin, P. Maki-Arvela, S. Leveneur, D.Yu. Murzin, T. Salmi, Batch and semi-batch partial oxidation of starch by hydrogen peroxide in the presence of iron tetrasulfophthalocyanine catalyst the effect of ultrasound and catalyst addition policy, ind. Eng. Chem. Res 50 (2011) 749—757. Copyright 2011 American Chemical Society).

The strong preference towards enone formation, which was realized by Gonzalez et al. employing iron(III) tetrasulfophthalocyanine and tBuOOH (Scheme 3.28, method B) [120], could be further improved by immobilization of the phthalocyanine complex on silica (method C). Under these conditions, p.-oxo dimeric species are suggested to be the active catalysts. 

The reactions of a-hydroxyalkyl radicals with Co P also took place via addition to the metal but, unlike the case of Fe P, the adducts were found to undergo heterolysis leading to reduction of the porphyrin to Co P. Another difference between the iron and cobalt porphyrins is in the stability of the methyl adduct CH3Co P was found to be stable even in the presence of O2. Related studies were carried out on the reactions of alkyl radicals with Co -tetrasulfophthalocyanine (tspc) and with Bi2r. Several cobalt-carbon adducts have been observed and in many cases they were found to decompose to yield the oxidized Co -complex. However, in the reaction of Co tspc with the radical derived from t-BuOH, the oxidized product was formed in neutral solutions but the reduced product, Co tspc, was formed in alkaline solutions. 

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