Oxidation Of Secondary Alcohols Research Articles

Electrocatalytic oxidation of 2-propanol on PtxIr100-x bifunctional electrocatalysts – A thin-film materials library study

Due to the high demand for renewable and infrastructure compatible energy conversion and storage technologies, research on organic fuel cells receives increasing interest again recently. Organic fuels such as alcohols provide an attractive avenue to overcome the drawbacks of hydrogen as an energy carrier. Particularly interesting are secondary alcohols that almost exclusively form ketones as the final oxidation product, as they can be utilized in “zero emission” concepts without CO2 as a by-product. The state-of-the-art electrocatalyst in secondary alcohol oxidation is Pt-Ru, which demonstrates low onset potentials for the oxidation of the most facile secondary alcohol isopropanol. Yet, the achievable current densities are still relatively low and decrease rapidly due to the formed product acetone, which can poison the catalyst surface over time. Therefore, there is an inevitable need for the development of novel electrocatalyst materials circumventing these challenges. In this study, we employ a high-throughput electrochemical approach coupled to on-line inductively-coupled plasma mass spectrometry to map the composition-dependent activity and stability of PtxIr100-x alloy electrocatalysts toward the electro-oxidation of isopropanol. The activity and stability of magnetron sputtered PtxIr100-x material libraries are studied in 0.1 M HClO4 both in the absence and presence of isopropanol. The highest current densities are achieved for the sample containing the least amount of Ir (3.4 at.%), with a continuous decrease with the increasing amount of Ir. The alloys are inactive towards the oxidation of isopropanol when the amount of Ir exceeded 80 at%. The presence of isopropanol also has a notable effect on stability: while dissolution rates do not change in the case of pure Pt and Ir, a significant increase in stability is observed for the PtxIr100-x thin-film samples at all applied upper potential limits. This is explained by the strong adsorption of acetone on the surface of the catalyst that inhibits the formation of surface oxides.

Quercetin as a Precursor for the Synthesis of Novel Nanoscale Cu (II) Complex as a Catalyst for Alcohol Oxidation with High Antibacterial Activity.

Quercetin (3,3′,4′,5,7-pentahydroxyflavone) is one of the dietary flavonoids, distributed in medicinal plants, vegetables, and fruits. Quercetin has the ability to bind with several metal ions to increase its biological activities. In the last two decades, quercetin has attracted considerable attention due to the biological and pharmaceutical activities such as antioxidant, antibacterial, and anticancer. In the present study, quercetin and ethanolamine were used for the synthesis Schiff base complex, which was characterized by IR, 1H NMR, and 13C NMR spectroscopy. The Schiff base has been employed as a ligand for the synthesis of novel nanoscale Cu (II) complex. The product was characterized by FT-IR spectroscopy, FESEM, and XRD. Significantly, the product showed remarkable catalytic activity towards the oxidation of primary and secondary alcohols. The antibacterial activity of the final product was assessed against Staphylococcus aureus (Gram‐positive) and Escherichia coli (Gram‐negative) bacteria using an inhibition zone test. The synthesized nanoscale Cu (II) complex exhibited a strong antibacterial activity against both Gram-positive and Gram-negative bacteria.

Green synthesis of sulfur‐doped g‐C3N4 nanosheets for enhanced removal of oxytetracycline under visible‐light irradiation and reduction of its N‐nitrosodimethylamine formation potential

AbstractBACKGROUNDIn this study, sulfur‐doped g‐C3N4 (SCN) nanosheets were synthesized using thiourea as a precursor, and then used to catalyze the degradation of oxytetracycline (OTC) under visible‐light irradiation. OTC was chosen as target contaminant because of it being an important precursor of N‐nitrosodimethylamine (NDMA).RESULTSThe removal of OTC was influenced by its initial concentration, initial pH, SCN dosage and water matrices. OTC (≤10 mg L−1) was almost completely removed in 40 min under the conditions of an initial pH of 7.0 and a SCN dose of 1.0 g L−1, and its degradation was well described by the pseudo‐first‐order kinetics model. Water matrices would also influence the degradation of OTC in the system. Electron paramagnetic resonance analysis and trapping experiments confirmed that the function of the radicals for OTC removal followed the order of •O2− > •OH > h+. Eight transformation products were determined during the degradation of OTC, it being removed through four pathways: methyl oxidization, demethylation, decarbonylation and secondary alcohol oxidation. SCN was stable in the system, as the removal efficiency of OTC was not significantly reduced even after three recycles. In addition, 55.5% of NDMA formation potential of OTC was reduced after SCN catalytic oxidation.CONCLUSIONSThe results imply that the visible‐light‐driven SCN catalytic oxidation is an effective technology not only for the removal of OTC but also for the reduction of NDMA formation potential. © 2021 Society of Chemical Industry

4CzIPN catalyzed photochemical oxidation of benzylic alcohols

A green photoredox oxidation of benzylic primary and secondary alcohols to aldehydes and ketones with air as an oxidant was reported. The oxidation shows broad substrate scope and excellent selectivity over benzylic alcohols to the aliphatic alcohols. Further mechanistic studies revealed a quinuclidine mediated HAT process, and blue LEDs promoted 4CzlPN (1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene) photoredox cycle were involved in our oxidation.

Исследование жидкофазного окисления алифатических спиртов при плазмохимической обработке воды

Plasma chemistry is part of the development of high technology that meets the modern requirements of greening and resource conservation. The study of physic-chemical laws and processes occurring in the zone of action of electric discharge plasma near the surface of a liquid is of high scientific and applied interest. In the study, developed and patented by a team of authors, plasma-chemical reactors were used, which implement the treatment of a liquid with both barrier and glow discharges near the surface of the liquid phase in a flow-through mode. Solutions of primary and secondary aliphatic alcohols were used as a model object of plasma-chemical treatment. As a result of the study, the mechanisms of liquid-phase oxidation of primary and secondary aliphatic alcohols during plasma-chemical treatment of water were proposed. The emission spectra of electric discharges at the gas-liquid interface in the presence of dissolved organic substances were obtained and analyzed. Spectral studies of electrodischarge plasma in the liquid-liquid zone confirmed the differing composition of the inorganic oxidation products of primary and secondary aliphatic alcohols. When deciphering the spectra of barrier and glow discharges, the characteristic emission bands of nitrogen N2, OH-radicals and nitric oxide, as well as lines of atomic hydrogen H and oxygen O were shown. In addition, the effect of the nature of the organic substances contained in the treated water on the characteristics of the electric discharge plasma was shown

Environmentally Benign Oxidation of Primary and Secondary Alcohols Catalyzed by Stabilized Gold Nanoparticles on Α-Hydroxy Amide-Functionalized Graphene Oxide

Multi-functionalized graphene oxide has been synthesized through an isocyanide-based multi-component reaction started by aminated graphene oxide and utilized as a support for the stabilization of gold nanoparticles. This composite has been used as a multifunctional, efficient and recyclable heterogeneous catalyst for the oxidation of various primary and secondary aliphatic and aromatic alcohols to the corresponding aldehydes and ketones in water under mild conditions in good to excellent yields.

An aerobic oxidation of alcohols into carbonyl synthons using bipyridyl-cinchona based palladium catalyst.

We have reported an aerobic oxidation of primary and secondary alcohols to respective aldehydes and ketones using a bipyridyl-cinchona alkaloid based palladium catalytic system (PdAc-5) using oxygen at moderate pressure. The PdAc-5 catalyst was analysed using SEM, EDAX, and XPS analysis. The above catalytic system is used in experiments for different oxidation systems which include different solvents, additives, and bases which are cheap, robust, non-toxic, and commercially available on the industrial bench. The obtained products are quite appreciable in both yield and selectivity (70–85%). In addition, numerous important studies, such as comparisons with various commercial catalysts, solvent systems, mixture of solvents, and catalyst mole%, were conducted using PdAc-5. The synthetic strategy of oxidation of alcohol into carbonyl compounds was well established and all the products were analysed using 1H NMR, 13CNMR and GC-mass analyses.

Superoxide Formation from Aqueous Reactions of Biogenic Secondary Organic Aerosols.

Reactive oxygen species (ROS) play a central role in aqueous-phase processing and health effects of atmospheric aerosols. Although hydroxyl radical (•OH) and hydrogen peroxide (H2O2) are regarded as major oxidants associated with secondary organic aerosols (SOA), the kinetics and reaction mechanisms of superoxide (O2•-) formation are rarely quantified and poorly understood. Here, we demonstrate a dominant formation of O2•- with molar yields of 0.01-0.03% from aqueous reactions of biogenic SOA generated by •OH photooxidation of isoprene, β-pinene, α-terpineol, and d-limonene. The temporal evolution of •OH and O2•- formation is elucidated by kinetic modeling with a cascade of aqueous reactions including the decomposition of organic hydroperoxides, •OH oxidation of primary or secondary alcohols, and unimolecular decomposition of α-hydroxyperoxyl radicals. Relative yields of various types of ROS reflect a relative abundance of organic hydroperoxides and alcohols contained in SOA. These findings and mechanistic understanding have important implications on the atmospheric fate of SOA and particle-phase reactions of highly oxygenated organic molecules as well as oxidative stress upon respiratory deposition.

Green, homogeneous oxidation of alcohols by dimeric copper(II) complexes

Three pyrazole derivatives, 3,5-dimethyl-1H-pyrazole (DMPz) (I), 3-methyl-5-phenyl-1H-pyrazole (MPPz) (II), and 3,5-diphenyl-1H-pyrazole (DPPz) (III), were prepared via reacting semicarbazide hydrochloride with the acetylacetone, 1-phenylbutane-1,3-dione, and 1,3-diphenylpropane-1,3-dione, respectively. Complexes 1–3 were isolated by reacting CuCl2·2H2O with I–III, respectively, and characterized by CHNS elemental analyses, FT-IR, UV-Vis, 1H and 13C NMR, EPR spectra, and TGA/DTA. Molecular structures of the pyrazole derivatives I–III and copper(II) complexes 2 and 3 were studied through single-crystal XRD analysis to confirm their molecular structures. Overlapping of hyperfine splitting in the EPR spectra of the dimeric copper(II) complexes 1–3 indicates that both copper centers do not possess the same electronic environment in solution. The copper(II) complexes are dimeric in solid state as well as in solution and catalyze the oxidation of various primary and secondary alcohols selectively. Catalysts 1–3 show more than 92% product selectivity toward ketones during the oxidation of secondary alcohols. Surprisingly primary alcohols, which are relatively difficult to oxidize, produce carboxylic acid as a major product (48%–90% selectivity) irrespective of catalytic systems. The selectivity for carboxylic acid rises with decreasing the carbon chain length of the alcohols. An eco-friendly and affordable catalytic system for oxidation of alcohols is developed by the utilization of H2O2, a green oxidant, and water, a clean and greener solvent, which is a notable aspect of the study.

Trinuclear ruthenium carbonyl complexes with salicylaldimine ligands as efficient catalysts for the oxidation of secondary alcohols

A series of novel trinuclear ruthenium carbonyl complexes [µ-ƞ2-2-OC6H4-CH=N-Ar)]2Ru3(CO)8 [Ar = Ph (8), C6H4-4-Me (9), C6H4-4-CF3 (10), C6H4-4-Cl (11), C6H3-2,6-Me2 (12), C6H3-2,6-Et2 (13)] and [µ-ƞ2-2-OC6H4-CH=N-C6H3-2,6-iPr2]Ru3(CO)9 (14) were designed and synthesized. All the seven novel complexes were fully characterized by elemental analysis, IR and NMR spectroscopy. Molecular structures of 8, 11, 13 and 14 were further confirmed by single-crystal X-ray diffraction. The catalytic performance of these complexes in the oxidation of secondary alcohols was explored and it was found the combination of such complexes and N-methylmorpholine-N-oxide (NMO) exhibits high catalytic activities for the oxidation of secondary alcohols, giving the corresponding carbonyl compounds in excellent yields.

Bioinspired Radical-Mediated Transition-Metal-Free Synthesis of N-Heterocycles under Visible Light.

A redox-active iminoquinone motif connected with π-delocalized pyrene core has been reported that can perform efficient two-electron oxidation of a class of substrates. The design of the molecule was inspired by the organic redox cofactor topaquinone (TPQ), which executes amine oxidation in the enzyme, copper amine oxidase. Easy oxidation of both primary and secondary alcohols happened in the presence of catalytic KOtBu, which could reduce the ligand backbone to its iminosemiquinonate form under photoinduced conditions. Moreover, this easy oxidation of alcohols under aerobic condition could be elegantly extended to multi-component, one-pot coupling for the synthesis of quinoline and pyrimidine. This organocatalytic approach is very mild (70 °C, 8 h) compared to a multitude of transition-metal catalysts that have been used to prepare these heterocycles. A detailed mechanistic study proves the intermediacy of the iminosemiquinonate-type radical and a critical hydrogen atom transfer step to be involved in the dehydrogenation reaction.

Magnetic spent coffee ground as an efficient and green catalyst for aerobic oxidation of alcohols and tandem oxidative Groebke–Blackburn–Bienaymé reaction

In this work, magnetic spent coffee ground as a green, inexpensive, and abundant material was synthesized and characterized by a variety of techniques, including X-ray diffraction pattern, thermal gravimetric analysis, scanning electron microscopy, energy-dispersive spectroscopy, inductively coupled plasma optical emission spectrometry, and Fourier transform infrared spectroscopy. The magnetic spent coffee ground was successfully utilized as a catalyst in aerobic oxidation of primary and secondary benzylic alcohols and tandem oxidative Groebke–Blackburn–Bienayme reaction.

Catalytic Selective Oxidation of Primary and Secondary Alcohols Using Nonheme [Iron(III)(Pyridine‐Containing Ligand)] Complexes

The selective oxidation of different primary and secondary alcohols to carbonyl compounds by hydrogen peroxide was found to be catalyzed in conversion ranging from good to excellent by an iron(III) complex of a pyridine‐containing macrocyclic ligand (Pc‐L), without the need of any additive. The choice of the counteranion (Cl, Br, OTf) appeared to be of fundamental importance and the best results in terms of selectivity (up to 99 %) and conversion (up to 98 %) were obtained using the well‐characterized [Fe(III)(Br)2(Pc‐L)]Br complex, 4c. Magnetic moments in solid‐state, also confirmed in solution ([D6]DMSO) by Evans NMR method, were calculated and point out to an iron metal center in the high spin state of 5/2. The crystal structure shows that the iron(III) center is coordinated by the four nitrogen atoms of the macrocycle and two bromide anions to form a distorted octahedral coordination environment. The catalytic oxidation of benzyl alcohol in acetonitrile was found occurring with better conversions and selectivities than in other solvents. The reaction proved to be quite general, tolerating aromatic and aliphatic alcohols, although very low yields were obtained for terminal aliphatic alcohols. Preliminary mechanistic studies are in agreement with a catalytic cycle promoted by a high‐spin iron complex.

Catalytic alcohol oxidation using cationic Schiff base manganeseIII complexes with flexible diamino bridge

Four Schiff base manganese(III) complexes with derivatives of [(R,R)-N,N’-bis(salicy1idene)-1,2-cyclohexanediaminato)] including substituents on salicylaldehyde such as 3-methoxy, 3,5-di-tert-butyl and 3,5-chloro were synthesized and characterized using a combination of IR, UV–Vis, and HR ESI-MS techniques. The catalytic activity of these complexes was tested in the oxidation of 1-phenylethanol to acetophenone, revealing very good performances for all of the four manganese complexes. The catalytic reactions were carried out in the presence of tert-butyl hydroperoxide (TBHP) as oxidant and imidazole as co-catalyst. Complex Mn-4, bearing electron withdrawing [(R,R)-N,N’-bis(3,5-di-chloro-salicylidene)-1,2-cyclohexanediaminato)] ligand was found to be the most stable of the tested Mn(III) complexes and was selected for the oxidation of several primary and secondary alcohols.

Catalytic Performance of a Magnetic Core-Shell Iron(II) C-Scorpionate under Unconventional Oxidation Conditions.

For the first time, herein is reported the use of a magnetic core-shell support for a C-scorpionate metallic complex. The prepared hybrid material, that consists on the C-scorpionate iron(II) complex [FeCl2{κ3-HC(pz)3}] (pz, pyrazolyl) immobilized at magnetic core-shell particles (Fe3O4/TiO2), was tested as catalyst for the oxidation of secondary alcohols using the model substrate 1-phenylethanol. Moreover, the application of alternative energy sources (e.g., ultrasounds, microwaves, mechanical or thermal) for the peroxidative alcohol oxidation using the magnetic heterogenized iron(II) scorpionate led to different/unusual outcomes that are presented and discussed.

Effective and selective aerobic oxidation of primary and secondary alcohols using CoFe2O4@HT@Imine‐CuII and TEMPO in the air atmosphere

In this study, we present a versatile and easy procedure for modifying a cobalt ferrite nanoparticle step by step. A new nanocatalyst was prepared via CuII immobilized onto CoFe2O4@HT@Imine. The catalyst was fully characterized by Fourier‐transform infrared (FT‐IR), energy‐dispersive X‐ray spectroscopy (EDX), field emission scanning electron microscopy (FE‐SEM), X‐ray diffraction (XRD), and vibrating sample magnetometer (VSM) analyses. The current procedure as a green protocol offers benefits including a simple operational method, an excellent yield of products, mild reaction conditions, minimum chemical wastes, and short reaction times. Without any significant reduction in the catalytic performance, up to five recyclability cycles of the catalyst were obtained. The optimization results suggest that the best condition in the oxidation of benzyl alcohol derivatives is 0.003 g of the CoFe2O4@HT@Imine‐CuII catalyst, TEMPO, at 70°C under solvent‐free condition and air.

Photochemical degradation kinetics and mechanisms of norfloxacin and oxytetracycline

The photochemical degradation of norfloxacin (NOR) and oxytetracycline (OTC) was investigated under ultraviolet (UV) irradiation. The results indicated that both NOR and OTC can be degraded, whereas the reaction rates decreased with increasing concentration of NOR and OTC. The degradation rates of NOR and OTC (5μM) were 0.0256min-1 and 0.0140min-1. Acidic conditions inhibited the degradation of NOR; however, alkaline conditions promoted the degradation of NOR. Meanwhile, the degradation of OTC was promoted by alkaline conditions but hardly affected by acidic conditions. In real water, the degradation of NOR was slower than that in ultrapure water, whereas the degradation of OTC was faster in real water. NOR produced five degradation products, with pathways mainly comprising hydroxylation and defluorination. OTC produced three degradation products, with its degradation pathways mainly consisting of deep oxidation, dehydration, and secondary alcohol oxidation. During the UV photolysis process, the mineralization rates of NOR and OTC (5μM) were 9.83% and 6.87% after 60-min irradiation. This work can provide a theoretical basis for understanding the migration and transformation behavior of antibiotics in the water environment.

Tungstate ion (WO42-) confined in hydrophilic/hydrophobic nanomaterials functionalized brönsted acidic ionic liquid as highly active catalyst in the selective aerobic oxidation of alcohols in water

A Brönsted acidic Ionic Liquid containing tungstate anion functionalized polysiloxane network (PMO-IL-WO42-) was synthesized by simple self-condensation of tungstic acid and zwitterionic organosilane precursor possessing both imidazolium and sulfonate groups. Characterization by scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy (FT-IR), X-ray powder diffraction (XRD), thermal gravimetric analysis TGA, nitrogen porosimetry, solid-state NMR spectroscopy and elemental analysis confirmed that both imidazolium cation and tungstate anion of zwitterion are successfully incorporated inside the organosilica framework. The catalytic activity of resulting hybrid PMO-IL- WO42- material was studied in the selective aerobic oxidation of primary and secondary alcohols using an atmospheric pressure of air in pure water. Due to the ionic liquid-based charged surface containing hydrophilic sulfonic acid and tungstate group, the synergistic hydrophilic/hydrophobic and redox effect of PMO-IL-WO42- as water-friendly catalyst facilitates and enhances the activity and selectivity toward the target oxidative products in water and proved to have a particularly broad substrate scope for reliable aerobic oxidation reaction. Furthermore, the catalyst showed outstanding stability and could be easily separated and reused at least ten reactions run under the same conditions as fresh catalyst without any loss of catalytic activity and product selectivity.

Application of The Dess-Martin Oxidation in Total Synthesis of Natural Products.

Dess-Martin periodinane (DMP), a commercially available chemical, is frequently utilized as a mild oxidative agent for the selective oxidation of primary and secondary alcohols to their corresponding aldehydes and ketones, respectively. DMP shows several merits over other common oxidative agents such as chromiumand DMSO-based oxidants; thus, it is habitually employed in the total synthesis of natural products. In this review, we try to underscore the applications of DMP as an effective oxidant in an appropriate step (steps) in the multi-step total synthesis of natural products.

Uncommon overoxidative catalytic activity in a new halo‐tolerant alcohol dehydrogenase

AbstractAlcohol dehydrogenases (ADH) are versatile and useful enzymes employed as biocatalysts, especially for the selective oxidation of primary and secondary alcohols, and for the reduction of carbonyl moieties. A new alcohol dehydrogenase (HeADH‐II) has been identified from the genome of the halo‐adapted bacterium Halomonas elongata, which proved stable in the presence of polar organic solvents and salt exposure. Unusual for this class of enzymes, HeADH‐II lacks enantiopreference and is capable of oxidizing both alcohols and aldehydes, enabling a direct overoxidation of primary alcohols to carboxylic acids. HeADH‐II was coupled with a NADH‐oxidase from Lactobacillus pentosus (LpNOX) to increase the process yields and allowing recycling of the cofactor. The enzymatic oxidation of primary alcohols was also paired with in situ condensation of the intermediate aldehydes with hydroxylamine to prepare the corresponding aldoximes, with particular attention to perillartine (a powerful sweetener), whose enzymatic synthesis starting from natural sources, leads to an equally natural product.