Heterogeneous Cu–Mn oxides mediate efficiently TEMPO-catalyzed aerobic oxidation of alcohols

Gao, Yang; Ma, Jiping; Wang, Wei; Zhao, Junfeng; Lin, Xuesong; Zhou, Lipeng; Gao, Xiaoyang

doi:10.1007/s10562-006-0168-x

Cited by 23 publications

(13 citation statements)

References 22 publications

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“…Other manganese‐based systems were applied for alcohol oxidation, namely, silica‐supported manganese dioxide (MnO 2 ) in the oxidation of benzyl alcohol under solvent‐free conditions,72 which yielded 88 % of acetophenone under MW for 20 s. However, this system required excess MnO 2 relative to the substrate (5:1 molar ratio), whereas in the present study we have achieved 72 % yield by using a maximum of 1 % molar ratio of catalyst relatively to substrate. Furthermore, mixed Mn–Cu or Mn–Co nitrates70 and heterogeneous Cu–Mn mixed oxides71 in combination with TEMPO have been employed for the selective aerobic oxidation of a variety of alcohols to the corresponding aldehydes and ketones under mild conditions. In our case, a significant yield increase was observed for the 1‐phenylethanol oxidation in the presence of 1 (from 36 % in the absence of TEMPO to 57 % in its presence; Table 2, Entries 5 and 14).…”

Section: Resultsmentioning

confidence: 99%

μ‐Chlorido‐Bridged Dimanganese(II) Complexes of the Schiff Base Derived from [2+2] Condensation of 2,6‐Diformyl‐4‐methylphenol and 1,3‐Bis(3‐aminopropyl)tetramethyldisiloxane: Structure, Magnetism, Electrochemical Behaviour, and Catalytic Oxidation of Secondary Alcohols

Alexandru¹,

Cazacu²,

Arvinte³

et al. 2013

Eur J Inorg Chem

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The reaction of 2,6-diformyl-4-methylphenol with 1,3-bis(3aminopropyl)tetramethyldisiloxane in the presence of MnCl 2 in a 1:1:2 molar ratio in methanol afforded a dinuclear μchlorido-bridged manganese(II) complex of the macrocyclic [2+2] condensation product (H 2 L), namely, [Mn 2 Cl 2 (H 2 L)-(HL)]Cl·3H 2 O (1). The latter afforded a new compound, namely, [Mn 2 Cl 2 (H 2 L) 2 ][MnCl 4 ]·4CH 3 CN·0.5CHCl 3 ·0.4H 2 O (2), after recrystallisation from 1:1 CHCl 3 /CH 3 CN. The coexistence of the free and complexed azomethine groups, phenolato donors, μ-chlorido bridges, and the disiloxane unit were well evidenced by ESI mass spectrometry and FTIR spectroscopy and confirmed by X-ray crystallography. The [a] "Petru

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Section: Resultsmentioning

confidence: 99%

μ‐Chlorido‐Bridged Dimanganese(II) Complexes of the Schiff Base Derived from [2+2] Condensation of 2,6‐Diformyl‐4‐methylphenol and 1,3‐Bis(3‐aminopropyl)tetramethyldisiloxane: Structure, Magnetism, Electrochemical Behaviour, and Catalytic Oxidation of Secondary Alcohols

Alexandru¹,

Cazacu²,

Arvinte³

et al. 2013

Eur J Inorg Chem

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“…The reported catalytic systems are exemplified by both homogeneous (Semmelhack et al 1984; Greene et al 2015) and heterogeneous procedures (Bolm and Fey 1999; Yang et al 2006). It is well-known that both of these procedures have their advantages and drawbacks.…”

Section: Introductionmentioning

confidence: 99%

“…A variety of investigations have revealed that 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) and its derivatives are some of the most efficient catalysts for the selective aerobic oxidation of alcohols to the corresponding carbonyl compounds (de Nooy et al 1996 ). The reported catalytic systems are exemplified by both homogeneous (Semmelhack et al 1984 ; Greene et al 2015 ) and heterogeneous procedures (Bolm and Fey 1999 ; Yang et al 2006 ). It is well-known that both of these procedures have their advantages and drawbacks.…”

Section: Introductionmentioning

confidence: 99%

TEMPO functionalized C60 fullerene deposited on gold surface for catalytic oxidation of selected alcohols

et al. 2017

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C60TEMPO10 catalytic system linked to a microspherical gold support through a covalent S-Au bond was developed. The C60TEMPO10@Au composite catalyst had a particle size of 0.5–0.8 μm and was covered with the fullerenes derivative of 2.3 nm diameter bearing ten nitroxyl groups; the organic film showed up to 50 nm thickness. The catalytic composite allowed for the oxidation under mild conditions of various primary and secondary alcohols to the corresponding aldehyde and ketone analogues with efficiencies as high as 79–98%, thus giving values typical for homogeneous catalysis, while retaining at the same time all the advantages of heterogeneous catalysis, e.g., easy separation by filtration from the reaction mixture. The catalytic activity of the resulting system was studied by means of high pressure liquid chromatography. A redox mechanism was proposed for the process. In the catalytic cycle of the oxidation process, the TEMPO moiety was continuously regenerated in situ with an applied primary oxidant, for example, O2/Fe3+ system. The new intermediate composite components and the final catalyst were characterized by various spectroscopic methods and thermogravimetry. Graphical abstractᅟ Electronic supplementary materialThe online version of this article (doi:10.1007/s11051-017-3857-z) contains supplementary material, which is available to authorized users.

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“…Benzaldehyde was the sole reaction product with 97% conversion of benzyl alcohol in 4 hours under reflux conditions, using excess of air or oxygen as stoichiometric oxidant. Similarly Yang et al [18] have studied the oxidation of benzyl alcohol to benzaldehyde catalysed by C -Mn oxide catalyst supported on carbon at 353 K. Yang et al [19] studied the oxidation of benzyl alcohol with 100% selectivity to benzaldehyde using MnO 2 as catalyst in the presence of 2,2,6,6-tetramethyl-piperidyl-1-oxy (TEMPO). About 23% and 36% benzyl alcohol was converted to benzaldehyde in 6 hours at 393 K with and without TEMPO.…”

Section: Introductionmentioning

confidence: 99%

Mixed-valence Manganese Oxide Catalysed Oxidation of Benzyl Alcohol and Cyclohexanol in the Liquid Phase

Ilyas

Saeed

Sadiq

et al. 2014

Progress in Reaction Kinetics and Mechanism

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Two types of mixed-valence manganese oxides were synthesised by a mechanochemical process in the solid phase by chemical reaction of manganese(II) chloride and potassium permanganate at room temperature. The prepared catalysts were characterised by surface area and pore size, particle size, XRD analyses, SEM analyses and oxygen content measurements. These oxides were used as catalysts for oxidation of benzyl alcohol and cyclohexanol in the presence of solvent and also in solvent-free conditions using molecular oxygen as oxidant. The oxidation reactions were heterogeneous in nature where the catalysts were separated from the reaction mixture by simple filtration. Reaction took place in two steps according to the Langmuir -Hinshelwood mechanism. Benzyl alcohol/cyclohexanol and oxygen adsorb at the surface of the catalyst in the first step followed by reaction between adsorbed benzyl alcohol/cyclohexanol in second step. 69.8 kJ mol -1 and 140.8 kJ mol -1 were calculated as the activation energy for benzyl alcohol and cyclohexanol in n-octane as the solvent respectively, with values of 65.1 and 76 kJ mol -1 for benzyl alcohol and cyclohexanol in solvent-free conditions respectively.

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Heterogeneous Cu–Mn oxides mediate efficiently TEMPO-catalyzed aerobic oxidation of alcohols

Cited by 23 publications

References 22 publications

μ‐Chlorido‐Bridged Dimanganese(II) Complexes of the Schiff Base Derived from [2+2] Condensation of 2,6‐Diformyl‐4‐methylphenol and 1,3‐Bis(3‐aminopropyl)tetramethyldisiloxane: Structure, Magnetism, Electrochemical Behaviour, and Catalytic Oxidation of Secondary Alcohols

μ‐Chlorido‐Bridged Dimanganese(II) Complexes of the Schiff Base Derived from [2+2] Condensation of 2,6‐Diformyl‐4‐methylphenol and 1,3‐Bis(3‐aminopropyl)tetramethyldisiloxane: Structure, Magnetism, Electrochemical Behaviour, and Catalytic Oxidation of Secondary Alcohols

TEMPO functionalized C60 fullerene deposited on gold surface for catalytic oxidation of selected alcohols

Mixed-valence Manganese Oxide Catalysed Oxidation of Benzyl Alcohol and Cyclohexanol in the Liquid Phase

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