TEMPO‐Copper(II) Diimine‐Catalysed Oxidation of Benzylic Alcohols in Aqueous Media

In situ generated copper(II)‐diimine complexes combined with TEMPO (2,2,6,6‐tetramethylpiperidinyl‐1‐oxyl radical) were studied in the oxidation of benzylic alcohols, the focus being on enviromentally benign reaction conditions. In this respect, reactions were studied in aqueous alkaline solutions and dioxygen was used as an end oxidant. This simple catalytic system turned out to be highly efficient and selective in the oxidation of primary and secondary benzylic alcohols to their corresponding carbonyl compounds. Under optimised reaction conditions [5 mol % of TEMPO, 3 mol % of copper(II ) diimine, pH 12.6–13.5, 80 °C, 10 bar O₂] benzyl alcohol was quantitatively and selectively oxidised to benzaldehyde. According to ESI‐MS studies, coordination of TEMPO, as well as deprotonated benzyl alcohol to the parent copper‐diimine complex in aqueous solutions is feasible. Supported by these observations a plausible reaction mechanism is proposed for the oxidation reaction.     

Liquid‐Phase Aerobic Oxidation of Benzyl Alcohol Catalyzed by Pt/ZrO2

The oxidation of benzyl alcohol by molecular oxygen in the liquid phase and catalyzed by Pt/ZrO2 using n‐heptane as the solvent was studied. Pt/ZrO₂ was very active and 100 % selective for benzyl alcohol conversion to benzaldehyde. The catalyst can be separated by filtration and reused. No leaching of Pt or Zr into the solution was observed. Typical batch reactor kinetic data were obtained and fitted to the Langmuir‐Hinshelwood, Eley‐Rideal and Mars‐van Krevelen models of heterogeneously catalyzed reactions. The Langmuir‐Hinshelwood model was found to give a better fit. The rate‐determining step was proposed to involve direct interaction of an adsorbed oxidizing species with the adsorbed reactant or an intermediate product of the reactant. H₂O₂ was also proposed to be an intermediate product. n‐Heptane was found to be an appropriate solvent in this reaction system.     

Aerobic Oxidation of Benzylic Alcohols in Water by 2,2,6,6‐Tetramethylpiperidine‐1‐oxyl (TEMPO)/Copper(II) 2‐N‐Arylpyrrolecarbaldimino Complexes

Novel copper(II) 2‐N‐arylpyrrolecarbaldimine‐based catalysts for the aerobic oxidation of benzylic alcohols mediated by the 2,2,6,6‐tetramethylpiperidine‐1‐oxyl (TEMPO) radical are reported. The catalytic activity for both synthesized and in situ made complexes in alkaline water solutions was studied revealing high efficiency and selectivity (according to GC selectivity always >99%) for both of these catalytic systems. For example, quantitative conversion of benzyl alcohol to benzaldehyde can be achieved with the in situ prepared bis[2‐N‐(4‐fluorophenyl)‐pyrrolylcarbaldimide]copper(II) catalysts in 2 h with atmospheric pressure of O₂ at 80 °C. Interestingly, these catalysts can utilize dioxygen as well as air or hydrogen peroxide as the end oxidants, producing water as the only by‐product.     

Effect of Surface Treatment on the Selective Photocatalytic Oxidation of Benzyl Alcohol into Benzaldehyde by O2 on TiO2 Under Visible Light

The photocatalytic oxidation of benzyl alcohol into benzaldehyde proceeded with high conversion and selectivity on a TiO₂ photocatalyst by O₂ under visible light irradiation. Surface complex formed by the interaction of benzyl alcohol with the Ti sites and/or surface OH groups of TiO₂ play an important role in the absorption of visible light and unique selective photocatalytic reaction.     

Fluorous biphase oxidation of ethyl benzene and benzyl alcohol catalyzed by perfluoroalkyl phthalocyanine complexes

BACKGROUND: Ketones and aldehydes are important organic chemicals as intermediates for the pharmaceutical and fine‐chemical industries. The existing oxidation reactions to obtain ketones and aldehydes are no longer sustainable because of the large amount of waste generated and use of stoichiometric reagents: a cleaner catalytic oxidation system needs to be developed. RESULTS: The experimental results show that cobalt (II) tetra‐(perfluorohexyl) phthalocyaninate delivered a high catalytic activity for the oxidation of ethyl benzene (35% conversion and 86% selectivity to acetophenone) at 90 °C under ambient pressure of oxygen. The catalyst could be recycled for at least four runs. For the oxidation of benzyl alcohol to benzaldehyde, a conversion of 6% was achieved but with a selectivity of 100% at 90 °C under 2 × 10⁵ Pa O₂. CONCLUSION: Perfluoroalkyl metallophthalocyanines can be used for the fluorous biphasic oxidation of ethyl benzene and benzyl alcohol with molecular oxygen. The cobalt (II) tetra‐(perfluorohexyl) phthalocyaninate exhibited the highest catalytic activity for the oxidation of ethyl benzene. The catalytic oxidation of benzyl alcohol using our method may be feasible in industrial applications. Copyright © 2009 Society of Chemical Industry     

Microwave-accelerated solvent-free aerobic oxidation of benzyl alcohol over efficient and reusable manganese oxides

A new facile and cost-effective process involving the solvent-free oxidation of benzyl alcohol using molecular oxygen as oxidant under controlled microwave irradiation has been developed for the production of chlorine-free benzaldehyde. Influence of different catalyst parameters (different manganese oxides and other kinds of transition metal oxides) and reaction conditions (reaction period and temperature) on the process performance has been studied. Under optimized reaction conditions, the MnO₂ catalyst showed a superior catalytic performance in the highly selective oxidation of benzyl alcohol as compared to other manganese oxide materials such as MnO, Mn₂O₃ and Mn₃O₄. Moreover, a very stable catalytic activity as a function of cycling test was observed for the MnO₂ catalyst.     

Aerobic oxidation of alcohols over Au/TiO2: An insight on the promotion effect of water on the catalytic activity of Au/TiO2

The unique and significant promotion effect of water has been evidenced by the selective oxidation of benzyl alcohol to benzaldehyde over Au/TiO₂ catalysts. Water has dual promotional functions in the reaction system: to help form unique microdroplets in a multiphase reaction system and to assist the oxygen adsorption and activation. The conversion of benzyl alcohol at a molar ratio of water to solvent (p-xylene) of 7 is 7 times higher than in the absence of water. The present work has highlighted the potential of Au/TiO₂ catalysts in aerobic oxidation of alcohols in the unique multiphase reaction system with water as promoting solvent.     

Solvent-Free Selective Oxidation of Benzyl Alcohol and Benzaldehyde by tert-Butyl Hydroperoxide Using MnO- 4-Exchanged Mg–Al–Hydrotalcite Catalysts

MnO^- ₄ (0.4 mmol/g)-exchanged Mg-Al-hydrotalcite is an active and highly selective catalyst for the oxidation of benzyl alcohol to benzaldehyde by tert-butyl hydroperoxide under reflux in the absence of solvent. It also shows high activity for the oxidation of benzaldehyde to benzoic acid. The higher the Mg/Al ratio, the higher is the catalytic activity (in both the reactions) and basicity of the hydrotalcite catalyst.     

Continuous gas–liquid aerobic oxidation of toluene catalyzed by [T(p-Cl)PPFe]2O in a series of three stirred tank reactors

The liquid-phase catalytic aerobic oxidation of toluene by [T(p-Cl)PPFe]₂O was studied in a series of three stirred tank reactors. The effects of operation mode (including semi-batch and continuous operation), reaction temperature, catalyst concentration, average residence time, and air flow rate on the oxidation process were examined. The experimental results showed that continuous oxidation had no advantage over the total yield and selectivity of benzaldehyde and benzyl alcohol in comparison with semi-batch oxidation. And the reaction temperature was the most significant factor influencing on continuous oxidation of toluene. It is also found that adopting sequentially decreased temperature in the three series reactors could improve the yield and selectivity of benzaldehyde and benzyl alcohol in this process. Under which at the higher conversion of toluene, the total yield to benzaldehyde and benzyl alcohol increased 17.05% or 43.62% respectively in comparison with adopting sequentially increased or same temperature in the three series reactors.     

Electrooxidation of benzyl alcohol at high surface area nickel (NiS x ) electrodes in alkaline solution

The heterogeneous catalytic redox behaviour of NiS _x deposited electrodes was investigated with and without benzyl alcohol in KOH solution using cyclic voltammetry and linear sweep voltammetry. The limiting current density for benzyl alcohol oxidation on a NiS _x electrode was 22 times larger than that on a polished nickel electrode. The experimental results in galvanostatic electrolysis using fractional factorial design showed that the main and interaction effects of benzyl alcohol concentration, temperature, and OH^– concentration are the key variables influencing the selectivity of benzaldehyde formation during electrolysis.     

Electrocatalytic oxidation of benzyl alcohol in alkaline medium on RuO2-coated titanium electrode

The heterogeneous electrocatalytic redox behaviour of RuO₂ electrodes fabricated by thermal decomposition is investigated with and without benzyl alcohol using cyclic voltammetric and potentiodynamic techniques. The cyclic voltammetric results show that benzyl alcohol oxidation is mediated by perruthenate ion electrogenerated at the electrode surface. Evaluation of kinetic parameters in relation to Tafel lines allows the postulation of a plausible reaction scheme in which benzyl alcohol adsorbs on the RuO₂ electrode surface and the rate determining step is chemical reaction between perruthenate and adsorbed species. The reaction orders with respect to benzyl alcohol and OH^– concentrations are 0.85 and 1, respectively. The results in galvanostatic electrolysis show that the major product for benzyl alcohol oxidation in an aqueous solution is benzaldehyde, and the organic yield is affected by such electrolysis conditions as t-butanol concentration, electrolysis current density, KOH concentration and electrolysis temperature.     

Synthesis of 2,5‐Diformylfuran and Furan‐2,5‐Dicarboxylic Acid by Catalytic Air‐Oxidation of 5‐Hydroxymethylfurfural. Unexpectedly Selective Aerobic Oxidation of Benzyl Alcohol to Benzaldehyde with Metal=Bromide Catalysts

The alcohol group of hydroxymethylfurfural (compound 1, HMF) is preferentially oxidized by dioxygen and metal/bromide catalysts [Co/Mn/Br, Co/Mn/Zr/Br; Co/Mn=Br/(Co+Mn) = 1.0 mol/mol] to form the dialdehyde, 2,5‐diformylfuran (compound 2, DFF) in 57% isolated yield. HMF can be also oxidized, via a network of identified intermediates, to the highly insoluble 2,5‐furandicarboxylic acid (compound 5, FDA) in 60% yield. For comparison, benzyl alcohol gives benzaldehyde in 80% using the same catalyst system. Over‐oxidation (to CO₂) of HMF is much higher than that of the benzyl alcohol but can be greatly reduced by increasing catalyst concentration.     

An efficient and universal solar interfacial photothermal reactor toward liquid phase oxidation

Photothermal catalysis has attracted great attention owing to high solar energy utilization efficiency, and great progress has been achieved in gas-phase catalysis. However, photothermal catalysis in liquid-phase shows a limited performance, due to high specific heat capacity of liquid. Herein, an interfacial photothermal catalytic (IPC) strategy applying an IPC leaf was designed for liquid-phase catalysis using benzyl alcohol oxidation as the model reaction. On even ground, the benzaldehyde generation rate (8.7 mmol g_cat⁻¹ h⁻¹) of the IPC system with Ce-doped MnO₂ as photothermal catalyst was almost 4.8 times and 3 times of bulk photothermal catalysis and the relative bulk thermal catalysis. Experimental results proved that this excellent catalytic performance could be attributed to both the high temperature achieved and the enhanced lattice oxygen activity by solar irradiation. This IPC system also exhibited good universality and long-term durability. Our work innovatively created a green strategy to obtain fine chemicals with only solar irradiation.     

Selective liquid-phase oxidation of toluene with molecular oxygen catalyzed by Mn-TiO2 under solvent-free conditions

In this paper, we reported the preparation, characterization, and catalytic performance of TiO₂ doped with Mn for the selective oxidation of toluene to benzyl alcohol and benzaldehyde without any solvent. The structure of the catalyst was determined by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), nitrogen adsorption–desorption analysis (Brunauer–Emmet–Teller [BET]), scanning electron microscope (SEM), transmission electron microscope (TEM), and mapping. The results demonstrated that the catalytic properties of Mn-TiO₂ were higher than those of pure Mn₃O₄ and TiO₂. The effects of reaction temperature, reaction time, oxygen pressure, and the amount of catalyst were studied. Under the optimal conditions, Mn-TiO₂ could afford 6.4% toluene conversion at a combined benzyl alcohol/benzaldehyde selectivity of 58.6%. Moreover, the catalyst can be repeated in the experiment for five times without significant loss of activity.     

Oxidation of alcohols with tert-butylhydroperoxide catalyzed by Mn (II) complexes immobilized in the pore channels of mesoporous hexagonal molecular sieves (HMS)

The oxidation of alcohols with tert-butylhydroperoxide (TBHP), in the presence of Mn²⁺ complexes immobilized in the pore channels of mesoporous hexagonal molecular sieves (HMS), were investigated. It was found that immobilized [Mn(bpy)₂]²⁺/HMS is an efficient catalyst for the oxidation of alcohols such as benzyl alcohol, n-hexanol and cyclohexanol. The effects of reaction time, amount of Mn²⁺ in the catalyst, type of substrates and oxidants in this catalysis system were investigated. At optimum conditions, TBHP is more efficient oxidant with respect to H₂O₂. Following order has been observed for the percentage of conversions of alcohols: benzylic >1° >2°.     

Galvanic deposition of silver on 80‐μm‐Cu‐fiber for gas‐phase oxidation of alcohols

Microstructured Ag‐based catalysts were developed by galvanically depositing Ag onto 80‐μm‐Cu‐fibers for the gas‐phase oxidation of alcohols. By taking advantages including large voidage, open porous structure and high heat/mass transfer, as‐made catalysts provided a nice combination of high activity/selectivity and enhanced heat transfer. The best catalyst was Ag‐10/80‐Cu‐fiber‐400 (Ag‐loading: 10 wt%; Cu‐fiber pretreated at 400 °C in air), being effective for oxidizing acyclic, benzylic and polynary alcohols. For benzyl alcohol, conversion of 94% was achieved with 99% selectivity to benzaldehyde at 300 °C using a high WHSV of 20 h^?1. Computational fluid dynamics (CFD) calculation and experimental result illustrated significant enhancement of the heat transfer. The temperature difference from reactor wall to central line was about 10–20 °C for the Ag‐10/80‐Cu‐fiber‐400, much lower than that of 100–110 °C for the Ag‐10‐Cu‐2/Al₂O₃ at equivalent conversion and selectivity. Synergistic interaction between Cu₂O and Ag was discussed, being assignable to the activity improvement. © 2014 American Institute of Chemical Engineers AIChE J, 60: 1045–1053, 2014     

Initial reaction steps in photocatalytic oxidation of aromatics

Transient reaction at 273 and 300 K was used to study the initial steps in the photocatalytic oxidation (PCO) of benzene, toluene, p-xylene, mesitylene, benzyl alcohol, benzaldehyde, and m-cresol adsorbed on a thin film of TiO₂ catalyst. Adsorbed aromatics were oxidized by O₂ photocatalytically in the absence of gas-phase aromatics, and the compounds remaining on the surface were characterized by temperature-programmed oxidation and desorption (TPO, TPD). Benzene and methyl benzenes oxidize rapidly at 273 or 300 K to form adsorbed intermediates that are more strongly adsorbed and much less reactive than the original aromatic, which is relatively weakly adsorbed on TiO₂. The catalyst is expected to be covered with these intermediates during steady-state reaction. The rates of PCO of benzene and methyl benzenes to CO₂ are slow relative to complete oxidation of alcohols or chlorinated hydrocarbons. The intermediates do not appear to be alcohols or aldehydes formed by oxidation of a methyl group, nor do they correspond to addition of an hydroxyl to the aromatic ring. Benzyl alcohol oxidizes photocatalytically to benzaldehyde and then to CO₂ and H₂O during PCO, but adsorbed m-cresol does not photocatalytically oxidize.     

Partial oxidation kinetics of m-hydroxybenzyl alcohol with noble metal catalysts in supercritical carbon dioxide

Partial oxidation of m-hydroxybenzyl alcohol was studied over several supported noble metal catalysts in a temperature range from 373 to 413 K, up to 2 MPa of oxygen pressure and 20 MPa of carbon dioxide pressure. The major product detected was m-hydroxybenzaldehyde. A charcoal supported palladium catalyst gave the highest yield of the aldehyde. For high temperature above 393 K and high oxygen pressure above 0.5 MPa, total oxidation was observed, which caused the selectivity of m-hydroxybenzaldehyde to decrease. Supercritical carbon dioxide medium seemed to improve heat dissipation of the reaction to allow the partial oxidation of m-hydroxybenzyl alcohol to occur under mild conditions. The partial oxidation of benzyl alcohol over a charcoal supported palladium catalyst was also examined for comparison and the major product formed was benzaldehyde. The conversion of benzyl alcohol and the selectivity to benzaldehyde was higher than those for the case of partial oxidation of m-hydroxybenzyl alcohol.     

Surface-modified Improvement in Catalytic Performance of Cr(salen) Complexes Immobilized on MCM-41 in Solvent-Free Selective Oxidation of Benzyl Alcohol

A series of typical methyl regulators were used to finely modify the Cr(salen) complex immobilized on MCM-41. Such immobilized complexes were effective catalysts for solvent-free selective oxidation of benzyl alcohol (BzOH) with 30% hydrogen peroxide (H₂O₂), and they all exhibited much higher catalytic performance than their homogeneous analogue. Simultaneously, the introduction of methyl regulators was found to significantly improve the catalytic performance of immobilized complexes by modifying their surface properties. The optimal BzOH conversion reached 65.0% with 100% selectivity to benzaldehyde (BzH).     

苯甲醛制备高纯苯甲醇的工艺研究

通过苯甲醛歧化反应制备苯甲醇,由硼氢化钾精制苯甲醇,同时使用气相色谱法对高纯苯甲醇中苯甲醛的含量进行测定,控制苯甲醛在苯甲醇中的含量,以达到提高苯甲醇品质的目的。该研究结论对高纯苯甲醇制备方法的选择提供重要依据。