Presence Of Metalloporphyrins Research Articles

Efficient and selective oxidation of tertiary benzylic C[sbnd]H bonds with O2 catalyzed by metalloporphyrins under mild and solvent-free conditions

The direct and efficient oxidation of tertiary benzylic CH bonds to alcohols with O2 was accomplished in the presence of metalloporphyrins as catalysts under solvent-free and additive-free conditions. Based on effective inhibition on the unselective autoxidation and deep oxidation, systematical investigation on the effects of porphyrin ligands and metal centers, and apparent kinetics study, the oxidation system employing porphyrin manganese(II) (T(2,3,6-triCl)PPMn) with bulkier substituents as catalyst, was regarded as the most promising and efficient one. For the typical substrate, the conversion of cumene could reach up to 57.6% with the selectivity of 70.5% toward alcohol, both of them being higher than the current documents under similar conditions. The superiority of T(2,3,6-triCl)PPMn was mainly attributed to its bulkier substituent groups preventing metalloporphyrins from oxidative degradation, its planar structure favoring the interaction between central metal with reactants, and the high efficiency of Mn(II) in the catalytic transformation of hydroperoxides to alcohols.

Dynamics of Changes in Composition and Stability of the Heavy Oil Sampled from the Usinskoye Oil Field as a Result of Formation Treatment with a Sol-Forming EOR System

The paper deals with a sol-forming system for oil recovery enhancement (EOR system) used to increase the rate of heavy oil displacement. The effect of sol-forming EOR system during the heavy oil displacement on the composition and stability of oil sampled from the Usinskoye oil field of Russia is investigated. The composition of a crude oil also plays an important role in changing its stability. The work is aimed to investigate stability of heavy crude oil in regards to asphaltene precipitation. For asphaltene toluene/n-heptane solutions, the aggregation stability of asphaltenes based on сhange in the optical density with time is investigated via spectrophotometry. SARA analysis is used to characterize the compositions of heavy oils. First, the content of asphaltenes precipitated from the oil samples is determined and then the samples of deasphalted crude oil (maltenes) are analyzed by the method of liquid adsorption chromatography for the purpose to study the composition of oil sampled from the wells before and after their treatment with the sol-forming EOR system. It is found out that the treatment of reservoir crude oil with the sol-forming EOR system results in changes in composition of saturated, aromatic hydrocarbons, resins, and asphaltenes (SARA components) and aggregative stability of produced oil. The results obtained showed that the aggregative stability of heavy oil depends not only on the content of SARA components in the dispersion medium but on the presence of metalloporphyrins in the oil. Metalloporphyrins could act as inhibitors of asphaltene precipitation, which is an additional factor responsible for the stabilization of the oil dispersed system

Redox activity of nickel and vanadium porphyrins: a possible mechanism behind petroleum genesis and maturation?

The presence of metalloporphyrins in crude oil has been known for many years. In contrast, their role on the physical–chemical properties is only now beginning to be understood. In this study, we test using high-level ab initio calculations, the hypothesis of a possible redox catalytic activity of vanadium and nickel metalloporphyrins in crude oil, illustrated by the oxidation of methanol to formaldehyde and hydrogen dissociation, respectively. This process which may take place during petroleum genesis and maturation, explains some of its physical–chemical properties, such as polar chains, the absence of alcohols, the trapping of porphyrins within macromolecular aggregates.

Mechanism of Propylene Epoxidation via O2 with Co‐Oxidation of Aldehydes by Metalloporphyrins

Propylene epoxidation by O2 plus acrolein in the presence of metalloporphyrins were investigated. According to the difference in initiation time and the reaction rate, a hypothesis metalloporphyrins or its center ion played a principal role in the initiation of reaction (redox reaction) rather than in the catalysis of PO generation reaction have been proposed, which was verified by the cyclic voltammogram of metalloporphyrins and UV/Vis spectra of samples in the time course study. Furthermore, the propylene epoxidation experiments using aldehydes easier to be initiated and corresponding blank control without metalloporphyrins were also investigated, and the results showed the same conclusion. On the other hand, the mechanism that the active species are peroxyacyl radical and peroxy acid was proposed through density function theory calculations, and in peroxyacyl radical path the intermediate generation process was the free radical addition of propylene by peroxyacyl radical. Moreover, optimum reaction paths were also carried out by computational calculations, the results showed that peroxyacyl radical was with higher activity than peroxy acid. As for peroxyacyl radical, the main addition site was the C1 of propylene, which was proved by the condensed Fukui function.

The role of metalloporphyrins on the physical-chemical properties of petroleum fluids

The presence of metalloporphyrins in crude oil has been known by many years now but their role on the physical-chemical properties of petroleum fluids, such as the aggregation of the high-molecular weight phases, remains unknown. In this paper, these properties are studied using different molecular modeling techniques (Molecular Dynamics, Semi-empirical PM7 and Density Functional Theory). This combined methodology allowed us characterizing the nature of these interactions, how it dominates the electronic structure of the stacked molecules and what is their participation on the formation of the nano-, micro- and macro-aggregates.

Efficient oxidative coupling of amines to imines catalyzed by manganese(III) meso-tetraphenylporphyrin chloride under ambient conditions

Highly efficient oxidative coupling of amines to imines by tert-butyl hydroperoxide (t-BuOOH) in the presence of metalloporphyrins has been reported. Manganese porphyrin showed excellent activity and selectivity for the oxidative coupling of amines to imines under ambient conditions. Moreover, a plausible mechanism involving high valence oxo intermediate has been proposed.

Aerobic oxidation of cumene to cumene hydroperoxide catalyzed by metalloporphyrins

A protocol for the aerobic oxidation of cumene to cumene hydroperoxide (CHP) catalyzed by metalloporphyrins is reported herein. Typically, the reaction was performed in an intermittent mode under an atmospheric pressure of air and below 130°C. Several important reaction parameters, such as the structure and concentration of metalloporphyrin, the air flow rate, and the temperature, were carefully studied. Analysis of the data obtained showed that the reaction was remarkably improved by the addition of metalloporphyrins, in terms of both the yield and formation rate of CHP while high selectivity was maintained. It was discovered that 4 or 5 h was the optimal reaction time when the reaction was catalyzed by monomanganese-porphyrin ((p-Cl)TPPMnCl) (7.20 × 10−5 mol/l) at 120°C with the air flow rate being 600 ml/min. From the results, we also found that higher concentration of (p-Cl)TPPMnCl, longer reaction time and higher reaction temperature were all detrimental to the production of CHP from cumene. Studies of the reaction kinetics revealed that the activation energy of the reaction (E) is around 38.9 × 104 kJ mol−1. The low apparent activation energy of the reaction could explain why the rate of cumene oxidation to CHP in the presence of metalloporphyrins was much faster than that of the non-catalyzed oxidation.

Highly efficient aerobic oxidation of oximes to carbonyl compounds catalyzed by metalloporphyrins in the presence of benzaldehyde

Highly efficient oxidation of oximes to carbonyl compounds by molecular oxygen with benzaldehyde as an oxygen acceptor in the presence of metalloporphyrins has been reported. The simple structural manganese porphyrin showed an excellent activity for the oxidative deoximation reactions of various oximes. Moreover, different factors influencing oximes oxidation, that is, catalyst, solvent, and temperature, have been investigated. A possible mechanism for the deoximation reaction has been proposed.

Metalloporphyrins in the biomimetic oxidative valorization of natural and other organic substrates

Cheap and abundant natural products can be transformed into products of higher commercial value. One of the approaches for the functionalization of organic compounds is their oxidation in the presence of an oxygen atom donor, under the influence of a suitable catalyst. Metalloporphyrins, with structures based on the well known meso-tetraphenylporphyrin (TPPH2), are amongst the catalysts commonly studied and have demonstrated to be efficient in the oxygenation of organic compounds. These transformations have been studied in the presence of different oxygen atom donors. However, our biomimetic oxidative approach is based on the use of clean and environmentally benign hydrogen peroxide in the presence of metalloporphyrins. This approach will be outlined in this review.

Oxygen atom transfer from carbonyl oxide to alkane catalyzed by metalloporphyrin

The reaction of singlet oxygen with diazofluorene in the presence of metalloporphyrin caused oxidation of hydrocarbons as well as sulfide and anisol in substantial yields. The active oxidizing species is probably a high valency metal oxo species(M O(porph)Cl) generated by an oxygen transfer from carbonyl oxide intermediate to M(porph)Cl.

Baeyer-Villiger oxidation of ketones catalyzed by iron(III) meso-tetraphenylporphyrin chloride in the presence of molecular oxygen

Efficient selective oxidation of ketones to lactones by molecular oxygen with benzaldehyde as an oxygen acceptor, in the presence of metalloporphyrins, has been reported. Iron(III) meso-tetraphenylporphyrin chloride ( Fe ( TPP ) Cl ) showed excellent activity and selectivity for oxidation of cyclohexanones under mild conditions. Moreover, different factors influencing ketones oxidation, e.g. catalyst, solvent, temperature and additive, have been investigated. The turnover number (TON) of the Fe ( TPP ) Cl catalyst could reach up to 71000 in a large scale oxidation of cyclohexanone. A plausible mechanism of ketone oxidation by molecular oxygen in the presence of metalloporphyrins and benzaldehyde was proposed.

Preparation of p-menthane hydroperoxide from p-menthane in presence of metalloporphyrins

The aerobic oxidation of p-menthane to p-menthane hydroperoxide (PMHP) in the presence of metalloporphyrins was investigated in an intermittent mode under an atmospheric pressure of air. Several important reaction parameters, such as the structure of metalloporphyrin, the air flow rate, and the temperature, were studied. The preliminary mechanism of the aerobic oxidation of p-menthane catalyzed by metalloporphyrins was also discussed. The results show that the reaction is greatly accelerated by the addition of metalloporphyrins at very low concentration, in terms of both the yield and formation rate of PMHP, and the high selectivity of PMHP is maintained during the reaction. Temperature of 120 °C and reaction time of around 5 h are the optimal conditions for the best result in the presence of 0.06 mmol/L monomanganeseporphyrins ((p-Cl)TPPMnCl). Furthermore, the yield of PMHP is increased remakably when the reaction is carried out under programmed temperature compared with the constant temperature. When the reaction is catalyzed by 0.06 mmol/L((p-Cl)TPPMnCl) at the air flow rate of 600 mL/min and 120 °C for 4 h, and then the temperature is reduced to 110 °C, for another 4 h, the yield of PMHP reaches 24.3%, which is higher than that of the reaction at a constant temperature of 120 °C or 110 °C for 8 h.

Highly efficient selective oxidation of alcohols to carbonyl compounds catalyzed by ruthenium (III) meso-tetraphenylporphyrin chloride in the presence of molecular oxygen

Efficient selective oxidation of alcohols to carbonyl compounds by molecular oxygen with isobutyraldehyde as oxygen acceptor in the presence of metalloporphyrins has been reported. Ruthenium (III) meso-tetraphenylporphyrin chloride (Ru(TPP)Cl) showed excellent activity and selectivity for oxidation of various alcohols under mild conditions. Moreover, different factors influencing alcohols oxidation, for example, catalyst, solvent, temperature, and oxidant, have been investigated. In large-scale oxidation of benzyl alcohol, the isolated yield of benzaldehyde of 89% was observed.

Catalysis of metalloporphyrins for selective hydroxylation of phenol by H2O2

Liquid phase catalytic selective hydroxylation of phenol to catechol and hydroquinone was carried out in the presence of metalloporphyrins using hydrogen peroxide as oxidant and water as solvent. Five kinds of metal tetra(p-chlorophenyl)porphrin ( T (p- Cl ) PPMCl , M = Fe , Co , Mn , Cu , Zn ) were studied. It was found that T (p- Cl ) PPFeCl had high catalytic activity and diphenol selectivity for the hydroxylation of phenol to catechol and hydroquinone. The influence of various reaction parameters, namely, reaction temperature, solvent, ratio of substrate and oxidant, substrate concentration, the amount of catalyst, reaction time and pH value were investigated systematically. When water was used as solvent (10 mL), the optimum conditions were following: pH = 7, the concentration of phenol was 0.3 g/mL, the molar ratio of phenol and H 2 O 2 was 1/2, the molar ratio of catalyst and phenol was 7/100000, the reaction temperature was 65°C and the reaction time was 1.5 h. Under above optimum conditions, the phenol conversion was up to 55.1%, and the selectivity of diphenol was almost up to 99.9%, the molar turnover numbers of the catalyst was about 7500. A possible mechanism was also proposed.

Leishmania pifanoiAmastigotes Avoid Macrophage Production of Superoxide by Inducing Heme Degradation

Whereas infections of macrophages by promastigote forms of Leishmania mexicana pifanoi induce the production of superoxide, infections by amastigotes barely induce superoxide production. Several approaches were employed to gain insight into the mechanism by which amastigotes avoid eliciting superoxide production. First, in experiments with nitroblue tetrazolium, we found that 25% of parasitophorous vacuoles (PVs) that harbor promastigotes are positive for the NADPH oxidase complex, in contrast to only 2% of PVs that harbor amastigotes. Second, confocal microscope analyses of infected cells labeled with antibodies to gp91phox revealed that this enzyme subunit is found in PVs that harbor amastigotes. Third, in immunoblots of subcellular fractions enriched with PVs from amastigote-infected cells and probed with antibodies to gp91phox, only the 65-kDa premature form of gp91phox was found. In contrast, subcellular fractions from macrophages that ingested zymosan particles contained both the 91- and 65-kDa forms of gp91phox. This suggested that only the immature form of gp91phox is recruited to PVs that harbor amastigotes. Given that gp91phox maturation is dependent on the availability of heme, we found that infections by Leishmania parasites induce an increase in heme oxygenase 1 (HO-1), the rate-limiting enzyme in heme degradation. Infections by amastigotes performed in the presence of metalloporphyrins, which are inhibitors of HO-1, resulted in superoxide production by infected macrophages. Taken together, we propose that Leishmania amastigotes avoid superoxide production by inducing an increase in heme degradation, which results in blockage of the maturation of gp91phox, which prevents assembly of the NADPH oxidase enzyme complex.

Oleic acid peroxidation in the presence of metallo-porphyrins

The influence of free bases of meso-tetrakis(3,5-di-tert-butyl-4-hydroxy-phenyl)porphyrins and meso-tetraphenylporphyrins and their complexes of Co , Ni , Cu , Pt upon the radical chain oxidation of oleic acid as model substrates for lipid peroxidation has been studied. It was shown that the introduction of the antioxidative phenolic fragment into the porphyrin ring leads to the dual activity of phenolic porphyrins when compared with their tetraphenyl substituted analogues in substrate oxidation. Free base phenolic porphyrins and their nickel, copper, platinum complexes demonstrate acute inhibitory effect upon oleic acid peroxidation due to the key role of 2,6-di-tert-butylphenol moities, whereas cobalt porphyrin exhibits dual activity associated with the presence of both the redox active metal center and phenolic group.

Metalloporphyrins as New Catalysts in the Highly Regioselective Conversion of Epoxides to Halohydrins with Molecular Halogen

The highly regioselective cleavage of epoxides by means of molecular iodine and bromine in the presence of metalloporphyrins affords vicinal iodohydrins and bromohydrins in high yields.

Metalloporphyrins as New Catalysts in the Highly Regioselective Conversion of Epoxides to Halohydrins with Molecular Halogen

The highly regioselective cleavage of epoxides by means of molecular iodine and bromine in the presence of metalloporphyrins affords vicinal iodohydrins and bromohydrins in high yields.

Metalloporphyrin-Catalyzed Oxidation of Alkanes with Molecular Oxygen in the Presence of Acetaldehyde

The aerobic oxidation of alkanes with acetaldehyde in the presence of metalloporphyrins gives the corresponding alcohols and ketones highly efficiently. Extremely high turnover numbers have been obtained for the oxidations of cyclohexane using cobalt, manganese, and ruthenium porphyrin catalysts bearing meso-pentafluorophenyl groups.

ChemInform Abstract: Peculiarities in the Catalytic Hydroxylation of Sitosterol and N,O‐ Diacetylsolasodine in the Presence of Metalloporphyrins.

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