Ferric chloride catalyzed photooxidation of alkanes by air in organic solvents

Shul’pin, Georgiy B.; Kats, M. M.

doi:10.1007/bf02097875

Cited by 48 publications

(19 citation statements)

References 4 publications

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“…Although we do not know how the iron-copper metal oxide promotes the reaction, transition metals salts are known to pull hydrogen out from organic compounds forming radicals and/or to promote the decomposition of peroxide species. [23,24] A dramatic change in conversion and selectivity was observed when a small amount (1% of toluene) of polar organic additives was added to the reaction media. As shown in Table 3, NBS and 1,1,2,2-tetrobromoethane promoted the reaction while phenol retarded it.…”

Section: Resultsmentioning

confidence: 99%

Liquid Phase Oxidation of Toluene to Benzaldehyde with Molecular Oxygen over Copper‐Based Heterogeneous Catalysts

Wang

et al. 2005

Adv Synth Catal

111

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We conducted the liquid phase oxidation of toluene with molecular oxygen over heterogeneous catalysts of copper-based binary metal oxides. Among the copper-based binary metal oxides, iron-copper binary oxide (Fe/Cu ¼ 0.3 atomic ratio) was found to be the best catalyst. In the presence of pyridine, overoxidation of benzaldehyde to benzoic acid was partially prevented. As a result, highly selective formation of benzaldehyde (86% selectivity) was observed after 2 h of reaction (7% conversion of toluene) at 463 K and 1.0 MPa of oxygen atmosphere in the presence of pyridine. These catalytic performances were similar or better than those in the gas phase oxidation of toluene at reaction temperatures higher than 473 K and under 0.5 -2.5 MPa. It was suggested from competitive adsorption measurements that pyridine could reduce the adsorption of benzaldehyde. At a long reaction time of 4 h, the conversion increased to 25% and benzoic acid became the predominant reaction product (72% selectivity) in the absence of pyridine. The yield of benzoic acid was higher than that in the Snia-Viscosa process, which requires corrosive halogen ions and acidic solvents in the homogeneous reaction media. The catalyst was easily recycled by simple filtration and reusable after washing and drying.

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Section: Resultsmentioning

confidence: 99%

Liquid Phase Oxidation of Toluene to Benzaldehyde with Molecular Oxygen over Copper‐Based Heterogeneous Catalysts

Wang

et al. 2005

Adv Synth Catal

111

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“…Because iron(III) chloride has been used as a homogeneous catalyst for the photooxidation of hydrocarbons [5,6], we compared the performance of Et 4 N[FeCl 4 ] with FeCl 3 , both homogeneous and heterogenized on silica gel. Results are shown in Table 7.…”

Section: Comparison Of Et 4 Nfecl 4 With Dissolved Fecl 3 and Fecl 3 mentioning

confidence: 99%

“…Another approach to heterogeneously catalyzed photooxidation makes use of heterogenized tetrachloroferrate(III) ion, and was introduced by Maldotti et al [3]. This approach is based on the ability of FeCl 3 to catalyze photooxidation processes homogeneously [4][5][6]. Iron(III) chloride, which is actually Fe 2 Cl 6 in solvents of low polarity, undergoes photodissociation, and the ability of the dissociated chlorine atoms to abstract hydrogen from a carbon atom, while not as strong as that of hydroxyl radicals or holes on TiO 2 or oxidized polyoxometallate anions, is still sufficient to initiate the oxidation of many substrates [7].…”

Section: Introductionmentioning

confidence: 99%

Photooxidation of Cyclohexane by Visible and Near-UV Light Catalyzed by Tetraethylammonium Tetrachloroferrate

et al. 2018

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Tetraethylammonium tetrachloroferrate catalyzes the photooxidation of cyclohexane heterogeneously, exhibiting significant photocatalysis even in the visible portion of the spectrum. The photoproducts, cyclohexanol and cyclohexanone, initially develop at constant rates, implying that the ketone and the alcohol are both primary products. The yield is improved by the inclusion of 1% acetic acid in the cyclohexane. With small amounts of catalyst, the reaction rate increases with the amount of catalyst employed, but then passes through a maximum and decreases, due to increased reflection of the incident light. The reaction rate also passes through a maximum as the percentage of dioxygen above the sample is increased. This behavior is due to quenching by oxygen, which at the same time is a reactant. Under one set of reaction conditions, the photonic efficiency at 365 nm was 0.018 mol/Einstein. Compared to TiO2 as a catalyst, Et4N[FeCl4] generates lower yields at wavelengths below about 380 nm, but higher yields at longer wavelengths. Selectivity for cyclohexanol is considerably greater with Et4N[FeCl4], and oxidation does not proceed past cyclohexanone.

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“…Photocatalytic oxidation has received enormousa ttention duringr ecent years because of its potential applications in environmental treatment [16][17] and the synthesis of fine chemicals. [18,19] Some important advances have been achieved in the UV or visible-light-triggered catalytic oxygenation of cyclohexane or other organic compoundsb yO 2 and the use of efficient photocatalysts including semiconductor oxides, [20][21][22][23][24][25] NaY zeolite, [26][27][28] transition metal complexes, [29][30][31] iron(III)c hloride, [32][33][34] copper(II) chloride, [35,36] decatungstate, [37][38][39][40][41][42][43] and so on. The following disadvantages,h owever,s till hindert he industrial application of these photocatalysts:i )most solid photocatalysts present unsatisfactory photocatalytic efficiency;i i) some efficient photocatalysts, like Fe porphyrin [29][30] and especially Os complexes, [31] lack of competitive advantage in terms of cost; iii)iron(III) or copper(II) chlorideisvery cheap and efficient photocatalyst,b ut it inevitably involves considerable amounts of chlorination;i v) the photocatalytic activity of decatungstate largelyr elies on UV-light irradiation.…”

Section: Introductionmentioning

confidence: 99%

Vanadium‐Substituted Tungstophosphoric Acids as Efficient Catalysts for Visible‐Light‐Driven Oxygenation of Cyclohexane by Dioxygen

Tang

et al. 2015

ChemCatChem

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This paper discloses that the oxygenation of cyclohexane by dioxygen (O2) to cyclohexanol and cyclohexanone over three vanadium‐substituted tungstophosphoric acids (PW11V1, PW10V2, PW9V3) can occur in MeCN under visible‐light irradiation, but provides very low cyclohexane conversion (0.8–2.4 %) with modest cyclohexanone selectivity (51–58.3 %). Importantly, an HCl aqueous solution was found to drastically promote this photooxygenation catalyzed by PW10V2 and especially PW9V3 acids, respectively providing approximately 20.4 and 23.4 % cyclohexane conversion and approximately 82.5 and 87.1 % cyclohexanone selectivity, with a concomitant formation of a small amount of chlorocyclohexane. However, such promoting effect was negligible in the PW11V1‐ photocatalyzed oxygenation and the other acids and the chlorine‐containing salts did not show any promotion effect on the present photocatalysis reaction. Notably, the HCl‐promoted photocatalytic oxygenation was significantly influenced by the amount of water. The cyclohexanone selectivity continuously and significantly increased with water amount, but photooxygenation efficiency drastically decreased if a slight excess amount of water was added. Based on these findings and the UV/Vis spectral and cyclic voltammetric measurements, a free‐radical mechanism initiated by the Cl atoms generated in the present photocatalysis system was proposed.

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Ferric chloride catalyzed photooxidation of alkanes by air in organic solvents

Cited by 48 publications

References 4 publications

Liquid Phase Oxidation of Toluene to Benzaldehyde with Molecular Oxygen over Copper‐Based Heterogeneous Catalysts

Liquid Phase Oxidation of Toluene to Benzaldehyde with Molecular Oxygen over Copper‐Based Heterogeneous Catalysts

Photooxidation of Cyclohexane by Visible and Near-UV Light Catalyzed by Tetraethylammonium Tetrachloroferrate

Vanadium‐Substituted Tungstophosphoric Acids as Efficient Catalysts for Visible‐Light‐Driven Oxygenation of Cyclohexane by Dioxygen

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