Regioselective Synthesis of Phenols and Halophenols from Arylboronic Acids Using Solid Poly(N‐vinylpyrrolidone)/ Hydrogen Peroxide and Poly(4‐vinylpyridine)/Hydrogen Peroxide Complexes

Solid hydrogen peroxide complexes based on poly(N‐vinylpyrrolidone) and poly(4‐vinylpyridine) were prepared and used as solid hydroxylating reagents. These solid hydrogen peroxide equivalents are found to be much safer, convenient and efficient reagent systems for the ipso‐hydroxylation of arylboronic acids to the corresponding phenols in high yields at a faster rate. The versatility of the reagents has been further expanded for the one‐pot synthesis of halophenols. Density functional theory calculations were carried out on hydrogen peroxide complexes of N‐ethylpyrrolidone and 4‐ethylpyridine as models to get a better understanding of structure and behavior of hydrogen peroxide complexes of the polymers poly(N‐vinylpyrrolidone) and poly(4‐vinylpyridine) compared to aqueous hydrogen peroxide.     

One‐Pot Conversion of Cephalosporin C to 7‐Aminocephalosporanic Acid in the Absence of Hydrogen Peroxide

The main drawback in the production of 7‐aminocephalosporanic acid (7‐ACA) at the industrial level is the inactivation of the enzymes implicated in the process due to the presence of hydrogen peroxide during the reaction. As an alternative, we have developed the conversion of cephalosporin C to 7‐ACA in a single reactor without the presence of hydrogen peroxide during the reaction, achieving more than 80% yield. In order to develop this process, D ‐amino acid oxidase (DAAO) was co‐immobilized with catalase (CAT), which is able to fully eliminate in situ the hydrogen peroxide formed by the neighbouring DAAO molecules. Thus, the product of the reaction is only α‐ketoadipyl‐7‐ACA. This system prevents the inactivation of the oxidase by hydrogen peroxide, solving the main problem of the enzymatic process. Moreover, we have found that α‐ketoadipyl‐7‐ACA is recognized as a substrate by glutaryl acylase (GAC) and hydrolyzed as long as glutaric acid is absent from the reaction medium (because it is able to inhibit the hydrolysis). The low stability of α‐ketoadipyl‐7‐ACA justifies the use of a single reactor, in which glutaryl acylase is already present when this substrate is generated. Thus, the whole process may (and must) be performed in a single step, and in the absence of hydrogen peroxide that could affect the stabilities of the involved enzymes.     

Kinetic Model of Gas‐Liquid‐Liquid Reactive Extraction for Production of Hydrogen Peroxide

The kinetic aspects of the gas‐liquid‐liquid reactive extraction process for the production of hydrogen peroxide were investigated in a batch reactor. It was observed that the gas‐liquid reaction rate is strongly affected by mass transfer of oxygen across the liquid film and the reaction can be simplified to pseudo‐first order. The extraction rate is governed by both reaction and liquid‐liquid mass transfer, and is slightly lower than the reaction rate. In addition, a kinetic model of the reactive extraction process for the production of hydrogen peroxide was developed. Kinetic parameters under different conditions were determined by experiments. The data calculated from the kinetic model match experimental data well under different conditions for hydrogen peroxide production in gas‐liquid‐liquid reactive extraction.     

Chemo‐enzymatic epoxidation of linoleic acid: Parameters influencing the reaction

The effect of reaction parameters on lipase‐mediated chemo‐enzymatic epoxidation of linoleic acid was investigated. Hydrogen peroxide was found to have the most significant effect on the reaction rate and degree of epoxidation. Excess of hydrogen peroxide with respect to the amount of double bonds was necessary in order to yield total conversion within a short time period, as well as at temperatures above 50 °C to compensate for hydrogen peroxide decomposition. However, prolonged incubation with high excess of hydrogen peroxide leads to the accumulation of peracids in the final product. The reaction rate increased also with increasing hydrogen peroxide concentration (between 10 and 50 wt‐%); however, at the expense of enzyme inactivation. Linoleic acid was completely epoxidized when used at a concentration of 0.5–2 M in toluene at 30 °C, while in a solvent‐free medium, the reaction was not complete due to the formation of a solid or a highly viscous oily phase, creating mass transfer limitations. Increasing the temperature up to 60 °C also improved the rate of epoxide formation.     

Impact of chemical oxidation on biological treatment of a primary municipal wastewater. 1. Effects on cod and biodegradability

Municipal wastewaters taken from a primary sedimentation tank were subjected to different chemical oxidation processes (ozonation or UV radiation alone or combined with hydrogen peroxide) to observe the evolution of COD and BOD/COD ratios. Ozonation of wastewater led to different increases of COD level reduction depending on pH and carbonate‐bicarbonate ion concentrations. Direct photolysis or hydrogen peroxide alone were found to be inappropriate technologies. On the other hand, advanced chemical oxidation, that is, oxidation with ozone or UV radiation combined with hydrogen peroxide, increased COD level reduction only when wastewater was previously decarbonated. Thus, elimination of carbonate‐bicarbonate ions, increase of pH and addition of hydrogen peroxide (10^‐3 M) yield increases COD level reduction rates. Finally, preozonation also allows improvement of wastewater biodegradability.     

Recent advances,challenges and prospects of in situ production of hydrogen peroxide for textile wastewater treatment in microbial fuel cells

Application of the Fenton process for textile wastewater treatment is limited due to high treatment cost, substantially contributed by the un‐availability of cheap hydrogen peroxide. Therefore, alternative methods for hydrogen peroxide production are in demand. One such option is in situ hydrogen peroxide production using a wastewater based microbial fuel cell (WBMFC). However, not much have been published regarding in situ production of hydrogen peroxide for textile wastewater treatment in a WBMFC. Therefore, in this work the concept, advantages, challenges and prospects of using WBMFC to treat textile wastewater by simultaneously producing hydrogen peroxide (hence in situ hydrogen peroxide) and power are reviewed. The concept of WBMFC is the reduction of oxygen in the presence of electrons and protons from the anode chamber to produce hydrogen peroxide with simultaneous power production. This review confirms that use of dual chambers, proton exchange membrane, domestic or municipal wastewater/Geobacter Sulfurreducens or Shewanella species, pure graphite cathode, ammonia and heat treated carbon‐based anode can treat most textile wastewaters. However, single chamber WBMFCs can be used as a low power source for an electro‐Fenton reactor. Power produced can be used to provide energy for aeration required in the WBMFC, thus providing an integrated and sustainable solution for textile wastewater treatment. © 2014 Society of Chemical Industry     

Mechanism of the ClO2 generation from the H2O2‐HClO3 reaction

The development of chlorine containing species during the hydrogen peroxide‐based chlorine dioxide generation process has been determined. Accordingly, two distinct phases, namely the induction period and the steady‐state phase, were identified. In the induction period, it was observed that chloride and chlorous acid are generated, while chlorine, a byproduct from some methanol‐based processes, is not detectable. The absence of chlorine is explained by the fast reaction kinetics between hydrogen peroxide and chlorine, which results in the formation of chloride. In the steady‐state phase, due to the accumulation of chloride and chlorous acid during the induction period, the reaction between chloric acid and chlorous acid, which is responsible for the generation of chlorine dioxide in the hydrogen peroxide‐based ClO₂ process, becomes possible. Chloride is a catalyst in such a reaction.     

Oxidation of hydroquinone to p‐benzoquinone catalyzed by Cu(II) supported on chitosan flakes

Copper (sorbed on chitosan flakes) was used as a catalyst for the oxidation of hydroquinone, with dioxygen (from air) and hydrogen peroxide as oxidizing agents. The supported catalyst was very efficient at oxidizing hydroquinone into p‐benzoquinone. With hydrogen peroxide at pH 5.8, drastic oxidizing conditions led to the formation of subproducts. With a short contact time, together with the use of a low hydrogen peroxide concentration and a small amount of the catalyst, the formation of subproducts could be minimized. The influence of the catalyst/substrate and hydrogen peroxide/substrate ratios was investigated to determine optimum experimental conditions for a high initial oxidation rate and a high production of p‐benzoquinone. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3034–3043, 2006     

Catalytic Olefin Epoxidation With H2O2 in Supercritical CO2. Synergic Effect by Hexafluoroacetone and Manganese‐Porphyrins

The heterogeneous oxidation of cyclooctene with hydrogen peroxide catalyzed by manganese 5,10,15,20‐tetrakis(2′,6′‐dichlorophenyl)porphyrinate, in the presence of hexafluoroacetone hydrate as co‐catalyst, has been studied in supercritical carbon dioxide, at 40 °C and 20 MPa. Under proper conditions, a complete olefin conversion may be obtained with the formation of cyclooctene oxide as the sole product. Fixation by hexafluoroacetone into its perhydrate derivatives provides a useful system to solubilize hydrogen peroxide in supercritical carbon dioxide, and to hamper catalyst bleaching and oxidant decomposition. Moreover, in the presence of both manganese‐porphyrin and hexafluoroacetone, the reaction rates are enhanced. Among the factors that may increase yields and rate of conversion, the use of a Teflon‐coated steel reactor rather than an uncoated one proved to be quite relevant, thus indicating the occurrence of a parasite radical decomposition of hydrogen peroxide promoted by steel reactor walls.     

Decomposition of hydrogen peroxide in the presence of activated carbons with different characteristics

BACKGROUND: Catalytic ozonation promoted by activated carbon is a promising advanced oxidation process used in water treatment. Hydrogen peroxide generated as a by‐product from the reaction of ozone with some surface groups on the activated carbon or from the oxidation of some organic compounds present in the water being treated seems to play a key role in the catalytic ozonation process. Hydrogen peroxide decomposition promoted by two granular activated carbons (GAC) of different characteristics (Hydraffin P110 and Chemviron SSP‐4) has been studied in a batch reactor. The operating variables investigated were the stirring speed, temperature, pH and particle size. Also, the influence of metals on the GAC surface, that can catalyze hydrogen peroxide decomposition, was observed. RESULTS: Chemviron SSP‐4 showed a higher activity to decompose hydrogen peroxide than HydraffinP110 (70 and 50% of hydrogen peroxide removed after 2 h process, respectively). Regardless of the activated carbon used, hydrogen peroxide decomposition was clearly controlled by the mass transfer, although temperature and pH conditions exerted a remarkable influence on the process. Catalytic ozonation in the presence of activated carbon and hydrogen peroxide greatly improved the mineralization of oxalic acid (a very recalcitrant target compound). About 70% TOC (total organic carbon) depletion was observed after 1 h reaction in this combined system, much higher than the mineralization achieved by the single processes used. CONCLUSIONS: Of the two activated carbons studied, Chemviron SSP‐4 with an acidic nature presented a higher activity to decompose hydrogen peroxide. However the influence of the operating variables was quite similar in both cases. Experiments carried out in the presence of tert‐butanol confirmed the appearance of radical species. A kinetic study indicated that the process was controlled by the internal mass transfer and the chemical reaction on the surface of the activated carbon. The catalytic activity of hydrogen peroxide in oxalic acid ozonation promoted by activated carbon (O₃/AC/H₂O₂) was also studied. The results revealed the synergetic activity of the system O₃/AC/H₂O₂ to remove oxalic acid. Copyright © 2010 Society of Chemical Industry     

Comparison of Various Alkaline Solutions for H2S/CO2‐Selective Absorption Applied to Biogas Purification

Biogas is a common renewable energy resource. A very important stage of biogas upgrading, studied in the present work, is its purification from H₂S traces. The selective absorption of H₂S and CO₂ into oxido‐alkaline solutions containing hydrogen peroxide and into amine solutions was compared by performing absorption test runs in a cables‐bundle scrubber at 293.15 K and atmospheric pressure. The absorption rate and selectivity for H₂S over CO₂ were determined for various solute partial pressures, different alkaline absorbents and hydrogen peroxide concentrations in the scrubbing liquid, and different pH values. Higher H₂S‐selective absorption performances with oxido‐alkaline solutions than with amine solutions could be observed provided that the solution is at a low pH value (9.5) and contains a sufficient hydrogen peroxide concentration.     

Oxidation of several chlorophenolic derivatives by UV irradiation and hydroxyl radicals

The oxidation of some chlorophenols: 4‐chlorophenol, 2,4‐dichlorophenol, 2,4,6‐trichlorophenol, 2,3,4,6‐tetrachlorophenol, tetrachlorocatechol (3,4,5,6‐tetrachloro‐2‐hydroxy phenol) and 4‐chloroguaiacol (4‐chloro‐2‐methoxy phenol) has been studied via single photodecomposition produced by polychromatic UV irradiation, oxidation by hydroxyl radicals generated by Fenton's reagent (hydrogen peroxide plus ferrous ions), and degradation by hydroxyl radicals produced by combinations of UV irradiation plus hydrogen peroxide, and UV irradiation plus hydrogen peroxide and ferrous ions (photo‐Fenton system). These organics have been selected as models of chloro‐phenolic derivative pollutants present in wastewaters and groundwaters. The degradation levels obtained in each process are reported. The quantum yields in the single photodecomposition reaction and the rate constants between the chlorophenols and the hydroxyl radicals in the reaction with Fenton's reagent are determined. Finally, the additional contributions to the photodecomposition promoted by the radical reaction in the combined UV/H₂O₂ and photo‐Fenton systems are also evaluated. © 2001 Society of Chemical Industry     

Low‐temperature bleaching of cotton fabric with a binuclear manganese complex of 1,4,7‐trimethyl‐1,4,7‐triazacyclononane as catalyst for hydrogen peroxide

Bleaching of cellulose fabric with hydrogen peroxide is traditionally conducted under alkaline conditions at high temperature, which leads to greater energy consumption and fibre damage. In this study, a binuclear manganese complex of the ligand 1,4,7‐trimethyl‐1,4,7‐triazacyclononane as the catalyst for hydrogen peroxide bleaching was synthesised via a simplified method. Low‐temperature bleaching of cotton fabric with the manganese complex and the effect of key bleaching variables on the bleaching performance were investigated. Hydrogen peroxide could be catalysed to bleach cotton knitted fabric at a temperature as low as 60 °C by incorporating the complex in the bleaching solution. The whiteness index of the fabric bleached at low temperature was lower than that of fabric bleached at high temperature, but the bursting strength retention is much better for the fabric bleached at low temperature. The low temperature is energy‐saving and has environment‐friendly advantages over the traditional high‐temperature method.     

In‐line monitoring of hydrogen peroxide in two‐phase reactions using raman spectroscopy

Hydrogen peroxide is an environment‐friendly oxidizer, which is used in several chemical processes. However, safety necessitates the determination and control of the concentration of hydrogen peroxide during oxidation reactions. We propose a methodology to monitor hydrogen peroxide in disperse two‐phase reaction mixtures based on in‐line Raman spectroscopy. We compare indirect hard modeling (IHM), peak integration (PI), and partial least squares (PLS). Building predictive PLS and PI calibration models is challenging, whereas the IHM calibration is easy to develop. These methods show good accuracy for known samples (root mean square error of cross validation [RMSECV] of 0.3–0.7 wt %) compared to the classic titration method (RMSECV of 0.4 wt %). After calibration, inline monitoring during reaction is performed demonstrating that the concentration of hydrogen peroxide can be successfully monitored in a fast and reliable way by Raman spectroscopy. The IHM seems to give slightly better inline predictions. © 2017 American Institute of Chemical Engineers AIChE J, 63: 3994–4002, 2017     

Electrochemical preparation of poly(o‐toluidine) film and its application as a permselective membrane

Poly(o‐toluidine) films were electrochemically synthesized on Pt electrodes at a constant potential (0.75 V versus Ag/AgCl) from a deoxygenated aqueous solution of 0.1M toluidine dissolved in 0.1M KCl. To form permselective polymeric film electrodes, poly(o‐toluidine) films at different thicknesses were prepared by varying the amount of charge consumed during electrochemical polymerization. Then, experimental parameters (e.g., concentrations of monomer and electrolyte and pH of the phosphate buffer salt solution) affecting the polymeric film thickness were optimized. Permeation of the various electroactive and nonelectroactive species such as ascorbic acid, oxalic acid, hydrogen peroxide, lactose, sucrose, and urea through the optimized poly(o‐toluidine)‐coated electrodes was investigated using a chronoamperometric technique. From experimental results, it was found that a poly(o‐toluidine)‐coated electrode permitted the oxidation of hydrogen peroxide and prevented the permeation of the mentioned electroactive and nonelectroactive species. In other words, it was seen that this polymeric electrode responded to only hydrogen peroxide selectively. Thus, it has been claimed that a poly(o‐toluidine)‐coated Pt electrode can be used as a permselective polymeric membrane to overcome interference problems occurring in the hydrogen peroxide‐based biosensor applications. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 2141–2146, 1999     

Cyclodextrin Aldehydes are Oxidase Mimics

Cyclodextrins containing 6‐aldehyde groups were found to catalyse oxidation of aminophenols in the presence of hydrogen peroxide. The catalysis followed Michaelis–Menten kinetics and is related to the catalysis previously observed with cyclodextrin ketones. A range of different cyclodextrin aldehydes were prepared containing one, two or more aldehydes at the primary rim (6‐positions) or a ethoxy‐2‐al or propoxy‐3‐al at the secondary rim. 2‐O‐ethoxy‐2‐al‐β‐cyclodextrin ( 22 ) was found to be the best catalyst. The aldehydes are in many cases better catalysts than the ketones, because of their powerful covalent binding of hydrogen peroxide.     

Mass‐Spectrometric and Kinetic Studies on the Mechanism and Degradation Pathways of Titanium Salalen Catalysts for Asymmetric Epoxidation with Aqueous Hydrogen Peroxide

The composition and degradation of a highly active and enantioselective titanium salalen in situ catalyst for the asymmetric epoxidation of olefins with aqueous hydrogen peroxide was investigated. Kinetic data and ESI‐MS studies point to a mononuclear titanium salalen as the catalytically active species. By means of ESI‐MS and selective monodeuteration of the salalen ligand, the oxidative degradation was studied. Upon exposure to aqueous hydrogen peroxide, the amine functionality of the salalen ligand is converted to the hydroxylamine, followed by loss of water and generation of the inactive titanium‐salen complex. This transformation limits the activity of the catalyst in the epoxidation of less electron‐rich olefins, such as 1‐octene.     

Copper‐Catalyzed Peroxide Oxidation Testing for Tetraphenylborate Decomposition

Abstract

A new processing option, copper‐catalyzed hydrogen peroxide oxidation of tetraphenylborate under alkaline conditions, was demonstrated in laboratory testing. Laboratory‐scale tests were conducted to evaluate the use of copper‐catalyzed hydrogen peroxide oxidation to treat simulants of the Savannah River Site tank waste. The oxidation process involves the reaction of hydrogen peroxide with a copper catalyst to form hydroxyl free radicals. With an oxidation potential of 2.8 volts, the hydroxyl free radical is a very powerful oxidant, second only to fluorine, and will react with a wide range of organic molecules. The goal is to oxidize the tetraphenylborate completely to carbon dioxide, with minimal benzene generation. Testing was completed in a lab‐scale demonstration apparatus at the Savannah River National Laboratory. Greater than 99.8% tetraphenylborate destruction was achieved in less than three weeks. Offgas benzene analysis by a gas chromatograph demonstrated low benzene generation. Analysis of the resulting slurry demonstrated >82.3% organic carbon destruction. The only carbon compounds detected were formate, oxalate, benzene (vapor), carbonate, p‐terphenyl, quaterphenyl, phenol, and phenol 3‐dimethylamino.     

Enantioselective Vanadium‐Catalyzed Oxidation of 1,3‐Dithianes from Aldehydes and Ketones using β‐Amino Alcohol Derived Schiff Base Ligands

The asymmetric vanadium‐catalyzed oxidation of 1,3‐dithianes from aldehydes and ketones by β‐amino alcohol‐derived Schiff base ligands with two stereogenic centers was investigated. Using aqueous hydrogen peroxide as the oxidant and the Schiff base 3b as a chiral ligand, a variety of 1,3‐dithianes derived from aldehydes were easily converted into the corresponding mono‐sulfoxides in good yields (81–88%) with excellent enantioselectivities (up to 99% ee). Additionally, 99% ee was obtained for the enantioselective vanadium‐catalyzed oxidation of the 1,3‐dithianes derived from ketones. We found a slight kinetic resolution when using a higher ratio of hydrogen peroxide during the oxidation of the aldehyde‐derived 1,3‐dithianes but not in the ketone‐derived 1,3‐dithianes.     

Supported Sulfonic Acid as Green and Efficient Catalyst for Baeyer–Villiger Oxidation with 30% Aqueous Hydrogen Peroxide

Silica‐supported propylsulfonic acid is a very good heterogeneous catalyst for the Baeyer–Villiger oxidation of cyclic ketones to lactones with stoichiometric 30% aqueous hydrogen peroxide in 1,1,1,3,3,3‐hexafluoro‐2‐propanol as solvent.