Epoxidation Reaction Research Articles

Microblog‐Assisted Synthesis of Schiff Base Network Polymers for SO2/Epoxide Copolymerization and Thermal Degradation Kinetics of the Products

AbstractThis study successfully prepared three environmentally friendly Schiff base network (SNW) polymers, SNW‐1, SNW‐2, and SNW‐3, using melamine and aldehyde compounds as raw materials through a microwave‐assisted synthesis method. The SNW materials were applied to catalyze the copolymerization reaction of SO2 and epoxides. Through detailed analysis of the chemical structure and properties of SNW‐1, SNW‐2, and SNW‐3, their catalytic efficiency was thoroughly investigated. Three thermal degradation kinetic models, Flynn–Wall–Ozawa (FWO), Kissinger, and Coats–Redfern, were employed to calculate the kinetic parameters of the thermal degradation of poly(cyclohexene sulfite) (PCS). Potential thermal degradation mechanisms were speculated. Additionally, the Kissinger model accurately described the thermal degradation kinetics features of PCS. Based on experimental results and kinetic analysis, this paper elucidates the potential mechanism of the copolymerization reaction of SO2 and epoxides. The study indicates that microwave‐assisted synthesis exhibits convenience and high efficiency in preparing efficient catalysts, demonstrating significant potential across various application domains.

Schiff Base-Based Molybdenum Complexes as Green Catalyst in the Epoxidation Reaction: A Minireview.

Epoxides are class of cyclic ether and have been extensively used in petrochemicals and pharmaceuticals industries as raw materials. Due to this reasons, development of the synthetic strategy of epoxides are getting enormous interest among the research chemists. In terms of "development of the synthetic strategy", the use of a catalyst, especially, Schiff base-based complex is of potential interest due to alternative easy routes and significant advances in metal-mediated pathways giving rise to diverse degree of substrate-reagent interactions. In addition, the synthetic strategy that follows the 12 principles of green chemistry, particularly (i) reduce the use of organic solvent, especially toxic solvents, and (ii) increasing the use of catalysts to obtain selective and quick processes in terms of atom economy, are of great attention now a days. The present review encompasses the Schiff base-based molybdenum complexes as green catalyst in the epoxidation reaction. Molybdenum complexes have grown interest owing to lower cost, environmental protection and commercialization as well as its abundance in different metalloenzymes. On the other hand, molybdenum complexes speed up the O-O bond break of tert-butylhydroperoxide (TBHP); as a result, it accelerates the oxygen transfer process from TBHP to the olefin. This review mainly focused on the catalytic activity of molybdenum-based Schiff base complexes for the epoxidation reaction in water/solvent free condition.

DMAP Catalyzed Ring-Opening/Cycloaddition of Vinyl Oxiranes with Activated Ketone Compounds to Construct the 1,3-Dioxolane Skeletons.

The present work develops a DMAP-catalyzed [3 + 2] cycloaddition of vinyl oxiranes with activated ketone compounds, affording dioxolane derivatives with moderate to excellent yields. This approach represents the first Lewis base (LB)-catalyzed ring-opening reaction of vinyl epoxides, simultaneously providing a rare oxygen-containing active intermediate in this field. The gram-scale preparation and facile derivatization of the cycloadduct highlight the significant synthetic potential of this strategy.

Alkyl polyglycosides derived from α-olefins via Fisher glycosidation and their adsorption and aggregation behavior in aqueous solution

The effective and stable use of α-olefins is a topic of great research interest due to their abundant reserves, and the fact that the hydrolysis and epoxidation reaction of these substances produces hydroxyl group as a key linking group plays an important role in the synthesis of surfactants. Consequently, a series of alkyl polyglycosides (DC08PG, DC10PG, and DC12PG) were synthesized as non-ionic surfactants via the glycosidation reaction of long-chain 1, 2-vicinal diol with different carbon numbers and glucose. The results showed that 1, 2-vicinal diol exhibited increased reactivity in glycosidation due to their unique molecular structure. Furthermore, it was observed that the degree of polymerization (DP) achieved was notably elevated, registering at 1.63, surpassing the DP of 1.37 typically prepared using conventional methods. This enhancement was paralleled by a demonstrable increase in hydrophilicity, as evidenced by the hydrophile-lipophile balance number (HLB), resulting in a substantial improvement in the water solubility of the product, the transmission rate > 90 %. For adsorption and aggregation behavior, DC12PG showed a smaller cross-sectional area (Amin), larger saturation adsorption (Γmax), and could aggregate to form micelles at low concentrations, and short-term dynamic adsorption properties (DST) was prominent. At the same concentration, for foam properties, DC12PG with longer alkyl chains produced higher and more stable foam; for emulsification properties, the emulsification time was 298 s; for wetting properties, the contact angle was 61.59° in 30 s. This analysis will help to reveal the intrinsic connection between the molecular structure and properties of surfactants.

Precursor-Directed Biosynthesis of Panepoxydone Derivatives with Nitric Oxide Production Inhibitory Activity.

Panepoxydone is a natural NF-кB inhibitor isolated from basidiomycetes belonging to the genus Panus and Lentinus. It is biosynthesized from prenylhydroquinone through successive hydroxylation, epoxidation, and reduction reactions. In this study, we establish an efficient precursor-directed biosynthesis strategy for the structural expansion of panepoxydone based on its biosynthetic pathway. Supplementation of the panepoxydone-producing strain, Panus rudis, with various prenylhydroquinone analogues enabled the production of fourteen previously undescribed panepoxydone derivatives, panepoxyquinoid A-N (2-14). The obtained panepoxydone derivatives together with their parental molecules were evaluated for their inhibitory activity on LPS-induced NO production in RAW 264.7 cells. Compounds 1, 5-6, 10-11, and 14-15 displayed significant suppressive effects on LPS-induced NO production with IC50 values ranging from 4.3 to 30.1 μM.

Mixed-Linker Zr-Metal-Organic Framework with Improved Lewis Acidic Sites for CO2 Fixation Reaction Catalysis.

Applying the mixed-linker strategy in synthesizing metal-organic frameworks (MOFs) has drawn considerable attention as a heterogeneous catalyst owing to their easy synthesis and different functional ligands in their frameworks. Following this strategy, we have developed a mixed linker Zr(IV)-based MOF, [Zr6O4(OH)4(FUM)n(PZDC-NO2)6-n] (PZDC-NO2 = 4-nitro-3,5-pyrazoledicarboxylic acid, FUM = fumaric acid) denoted as MOF-801(PZDC-NO2) synthesized via this strategy which possess an electron-withdrawing group (-NO2) on secondary linkers. The MOF-801(PZDC-NO2) has been fully characterized via various analyses, such as Fourier transform infrared, powder X-ray diffraction, 13C/1H nuclear magnetic resonance, XPS, TGA, and N2 adsorption/desorption, SEM, EDX, etc. By considering the concurrent existence of acid-base active sites and the synergistic role of these sites, this mixed-linker MOF was used as a catalyst for the cycloaddition reaction of CO2 and epoxides under mild without-solvent conditions. MOF-801(PZDC-NO2) displays significant catalytic performance by producing the highest catalytic conversion of epoxide to cyclic carbonate (93%) with a turnover number of 130.7 in 8 h reaction time and 100 °C temperature under low-pressure CO2 pressure. The mixed-linker Zr-MOF exhibits exceptional stability and reusability, maintaining its structure and functionality after consecutive cycles of utilization. Finally, the reaction mechanism was further investigated by density functional theory calculations. The total energy of the reactants, intermediates, and products involved in the process.

Total biosynthesis of the medicinal triterpenoid saponin astragalosides.

Astragalus membranaceus has been used in traditional Chinese medicine for over 2,000 years. Its major active triterpenoid saponins, astragalosides, have attracted great attention due to their multiple health benefits and applications in medicine. Despite this, the biosynthetic machinery for astragalosides remains enigmatic. Here a chromosome-level genome assembly of A. membranaceus was generated. The identification of two tailoring enzymes required for astragaloside biosynthesis enabled the discovery of a triterpenoid biosynthetic gene cluster, leading to elucidation of the complete astragaloside biosynthetic pathway. This pathway is characterized by a sequence of selective hydroxylation, epoxidation and glycosylation reactions, which are mediated by three cytochrome P450s, one 2-oxoglutarate-dependent dioxygenase and two glycosyltransferases. Reconstitution of this biosynthetic machinery in Nicotiana benthamiana allowed for heterologous production of astragaloside IV. These findings build a solid foundation for addressing the sourcing issues associated with astragalosides and broaden our understanding of the diversity of terpene biosynthetic gene clusters.

Synthesis of Bio lubricant from Bhallataka oil

The demand for a renewable and biodegradable lubricant as a substitute for fossil fuel-based lubricant has increased due to strong environmental concerns and expanding regulations over contamination and pollution in the environment. This study investigated the potential of using Semecarpus anacardium L.f. oil, which was identified as a potential raw material for biodiesel, as a feed stock for bio lubricants. Epoxidation and hydrolysis reactions were used to synthesize bio-lubricant. Epoxidized SA L.f oil was made using peroxyformic acid, which was produced on the spot by reacting hydrogen peroxide and formic acid with sulfuric acid acting as a catalyst. The oxirane value of the oil was 3.77, indicating that the unsaturated bonds were almost entirely converted to oxirane, while the iodine value decreased from 90.7 to 2.01 mg I2/g. ESAO

Green Conversion of Epoxides to Cyclic Carbonates by Copper Nanocrystals Fabricated on Jute Tartaric Acid Composite Surface

AbstractThe synthesis of copper nanocrystals on tartaric acid jute composite surface is reported. The formation of nanocrystals is detected by FT IR, Powder X‐ray diffraction, SEM, and TEM analysis. The average size of the nanocrystals is found to be 500 nm. The reaction of the copper nanocrystals with CO2 resulted in a decrease in the size of the nanoparticles. Cycloaddition reaction of epoxides to cyclic carbonate is efficiently carried out by the copper nanocrystals on tartaric acid jute composite surface (CUNPJT) without using any cocatalyst and solvent. To the best of author's knowledge, this is the first example of copper nanocrystals catalyzing the cycloaddition of CO2 and epoxide.

Siloxane-based oligomer ligands of indium phosphide quantum dots for improving dispersion in a siloxane matrix

The ligands of indium phosphide (InP) quantum dots (QDs) were modified with siloxane-based oligomers in a two-step process to improve the dispersion of InP QDs in a siloxane-based matrix. Oleic acid ligands on InP QDs (InP-OA) were exchanged with 6-mercapto-1-hexanol. Then, the hydroxyl functional groups (–OH) of the ligands were induced to react with poly(dimethylsiloxane), diglycidyl ether terminated (PDMS-DGE) by a ring-opening reaction of epoxide. The chemical bonding between the hydroxyl groups and PDMS-DGE was confirmed by Fourier-transform infrared (FT-IR) spectroscopy. The synthesized InP QDs with PDMS-DGE ligands (InP-PDMS-DGE) were blended with acrylate-siloxane polymers to produce color conversion QD films. The photoluminescence (PL) intensity of the QD films with the InP-PDMS-DGE QDs was improved by 2.3 times compared with that of InP-OA QDs. The color conversion efficiency of the QD films was determined using a blue light-emitting diode (LED), and the QD film containing InP-PDMS-DGE QDs demonstrated a conversion efficiency of 21%, compared to a lower efficiency of 17% for a film containing InP-OA QDs. The stability of the InP-PDMS-DGE film was tested at 85°C with a relative humidity (RH) of 85%, demonstrating an improvement of 28% compared to that with an InP-OA film.

The Performance of Ethylene Partial Oxidation on Group IB Metal Stepped Surfaces

Group IB metal catalysts, particularly Ag, Au, and Cu, exhibit particular selectivity for ethylene oxide (EO) formation, while Ag demonstrating the highest performance so far. Previous studies have explored the EO formation mechanism on (100) and (111) surfaces of group IB metals, but the reaction mechanism on the (211) facet (analogous to the edge sites of a catalyst particle) remains poorly understood. Herein, we fill in the knowledge gap by analyzing ethylene partial oxidation to EO on the (211) surfaces of Ag, Au, and Cu through density functional theory (DFT) calculations, scaling relationship analysis, and microkinetic modeling. Our study demonstrates that the (211) surface decreases the energy barrier for the dissociation of oxygen molecules into oxygen atoms, while unfavorable for the production of EO. Therefore, we should preserve an appropriate concentration of (211) surface on the nanoparticles when designing catalysts for the ethylene epoxidation reaction.

Real-Time Simulation of the Reaction Kinetics of Supported Metal Nanoparticles.

A common issue with supported metal catalysts is the sintering of metal nanoparticles, resulting in catalyst deactivation. In this study, we propose a theoretical framework for realizing a real-time simulation of the reactivity of supported metal nanoparticles during the sintering process, combining density functional theory calculations, microkinetic modeling, Wulff-Kaichew construction, and sintering kinetic simulations. To validate our approach, we demonstrate its feasibility on α-Al2O3(0001)-supported Ag nanoparticles, where the simulated sintering behavior and ethylene epoxidation reaction rate as a function of time show qualitative agreement with experimental observation. Our proposed theoretical approach can be employed to screen out the promising microstructure feature of α-Al2O3 for stable supported Ag NPs, including the surface orientation and promoter species modified on it. The outlined approach of this work may be applied to a range of different thermocatalytic reactions other than ethylene epoxidation and provide guidance for the development of supported metal catalysts with long-term stability.

Complementary Tandem Reaction Manifolds and "Switch Mechanisms" in the Reaction of Epoxides with Selectfluor.

Tandem reactions are highly sought after transformations in organic synthesis as they accomplish multiple steps at once and can serve as golden keys unlocking mechanistic complexities. Reactions that operate through different mechanisms depending on the conditions ("switch mechanisms") are of intense interest to organic chemists as fonts of new reactivity. We report that Selectfluor can catalyze the rearrangement of 1,1-disubstituted epoxides, providing a new approach to benzylic fluorination. These results complement earlier work involving radical-cation-based ring opening of epoxides.

Triazine- and amino-functionalized poly(ionic liquid) heterogeneous catalyst for efficient CO2 conversion under mild conditions

The efficient conversion of atmospheric CO2 into high value-added chemicals remains a persistent challenge. In this study, a novel strategy for the fabrication of triazine- and amino-functionalized poly(ionic liquid)s (PILs) was reported. By virtue of the rich nitrogen species, the newly-developed PILs possessed great potential in CO2 conversion to produce high-value chemicals. The systematic investigation illustrated that rich-nitrogen PILs could promote the cycloaddition reaction of CO2 and epoxides through the intramolecular synergy of multiple active sites. Excellent conversion and selectivity were achieved under the mild conditions without any co-catalysts and solvents. In addition, PIL heterogeneous catalysts could be easily recovered and reused at least several times without obvious loss in activity. The density functional theory calculation demonstrated that the superior catalytic activity of rich nitrogen PILs was attributed to the synergistic effect of hydrogen bond donor and triazine ring in the catalytic process. Our finding thus presents a versatile platform for fabricating multi-functional heterogeneous catalysts for efficient CO2 conversion.

A tailored cytochrome P450 monooxygenase from Gordonia rubripertincta CWB2 for selective aliphatic monooxygenation.

Cytochrome P450 monooxygenases are recognized as versatile biocatalysts due to their broad reaction capabilities. One important reaction is the hydroxylation of non-activated C-H bonds. The subfamily CYP153A is known for terminal hydroxylation reactions, giving access to functionalized aliphatics. Whilst fatty derivatives may be converted by numerous enzyme classes, midchain aliphatics are seldomly accepted, a prime property of CYP153As. We report here on a new CYP153A member from the genome ofthe mesophilic actinobacterium Gordonia rubripertincta CWB2 as an efficient biocatalyst. The gene was overexpressed inEscherichia coli and fused with a surrogate electron transport system from Acinetobacter sp. OC4. This chimeric self-sufficient whole-cell system could perform hydroxylation and epoxidation reactions: conversions of C6-C14 alkanes, alkenes, alcohols and of cyclic compounds were observed, yielding production rates of, e.g., 2.69 mM h-1 for 1-hexanol and 4.97 mM h-1 for 1,2-epoxyhexane. Optimizing the linker compositions between the protein units led to significantly altered activity. Balancing linker length and flexibility with glycine-rich and helix-forming linker units increased 1-hexanol production activity to 350 % compared to the initial linker setup with entirely helical linkers. The study shows that strategic coupling of efficient electron supply and a selective enzyme enables previously challenging monooxygenation reactions of midchain aliphatics.

Epoxidation of Hybrid Oleic Acid Derived From Palm Oil and Waste Cooking Oil For Eco-Friendly Polyol Production

Background: Palm oil and waste cooking oil undergo functionalization by introducing epoxy groups onto their double bonds, which are subsequently opened to yield hydroxyl groups. Objectives: The objective of this paper is to produce epoxidized hybrid oleic acid with an applied heterogeneous catalyst for polyol feedstock. Methods: In situ peracids are generated during the reaction by mixing an acid (commonly acetic acid or formic acid) with hydrogen peroxide. Range Kutta 4th Order Method of numerical integration was used to develop kinetic modeling for reaction based on the mathematical model. Results: After 40 minutes of epoxidation reaction, the relative conversion to the oxirane percentage reached its maximum of 51%. Fourier transform infrared spectroscopy detected an absorption peak at 3300 cm-1, suggesting the presence of a hydroxyl group. Conclusion: Epoxidation of palm oil and waste cooking oil using in situ peracids is an efficient method for converting unsaturated fatty acids into epoxidized oils, which have significant industrial applications.

Benzo[a]pyrene: A carcinogen, its sources, adverse effects, and preventive measures

A polycyclic aromatic hydrocarbon called benzo[a]pyrene (B[a]P) is produced during incomplete burning of fuels. The most common way humans consume B[a]P is through food products, particularly grilled or smoked foods. B[a]P is also frequently detected in the sediments, soil, surface water, and air. Once bioactivated, it produces a highly reactive epoxide monomer that can create adducts by chemically reacting with biological molecules, such as DNA. B[a]P is implicated in various cancers due to its interaction with the aromatic hydrocarbon receptor (AhR). Apart from its detrimental impacts on development and reproduction, this substance also suppresses the immune system. Microbes, however, are critical to cleaning up the B[a]P-contaminated environment. This review focuses on forming B[a]P in different compartments of the environment and human surroundings, and the mechanisms responsible for its harmful effects and carcinogenic risk. This review also discusses the strategies for the deterioration of B[a]P.

Constructing Highly Efficient Catalysts for the 1‐Butene Epoxidation

AbstractEpoxides are high‐valued intermediates in the production of chemicals, pharmaceuticals, perfumes, and polymers. Given the growing demand for epoxides, it is imperative to develop more environmental friendly and sustainable routes instead of the chlorohydrin process. Notably, the direct utilization of hydrogen peroxide (H2O2) for the epoxidation reaction presents significant advantages from both environmental and economic perspectives. The review provides insights into both homogeneous and heterogeneous catalysts employed in the 1‐butene epoxidation using the green oxidant H2O2. Among the diverse range of catalysts, titanosilicate‐1 (TS‐1) has garnered extensive attention due to its exceptional selectivity and high oxygen atom utilization. The aim of this review is to illustrate various strategies for TS‐1 catalysts preparation that can lead to more versatile, higher‐performance, and greener epoxidation processes. Additionally, various potential approaches to enhance the catalyst performance of TS‐1 are highlighted, including (i) constructing specific coordination modes of Ti sites, (ii) regulating the microenvironment around Ti sites, and (iii) improving the accessibility of Ti sites. Furthermore, advances in molding TS‐1 catalysts are also introduced from the perspective of the industrialization. Finally, future research directions are discussed with emphasis on the application scope of TS‐1 to gain deeper insights into epoxidation process.

Allylic Epoxides Increase the Strain Energy of Cyclic Olefin Monomers for Ring-Opening Metathesis Polymerization.

Ring-opening metathesis polymerization (ROMP) is an effective method for synthesizing functional polymers, but since the technique typically relies on high ring strain cyclic olefins, the most common monomers are norbornene derivatives. The reliance on one class of monomer limits the obtainable properties of ROMP polymers. In this work, we investigate new bicyclic monomers synthesized via epoxidation of commercial dienes. DFT estimates of these monomers' ring strains suggests a significant increase in strain for cyclic olefins containing allylic epoxides. We found that the eight-membered (3,4-COO) and five-membered (CPO) cyclic olefins were particularly effective for ROMP. CPO was of especially intriguing due to its excellent polymerizability when compared to the limited reactivity of other five-membered rings. Unlike polynorbornenes, the resulting polymers of both monomers displayed glass transition temperatures well below room temperature. Interestingly, poly(3,4-COO) showed both high stereo- and regioregularity while poly(CPO) showed little regularity. Both polymers could be readily modified via post-polymerization ring-opening of the reactive allylic epoxides. With a high epoxide density in poly(CPO), CPO is an exciting new ROMP monomer that is easily synthesized, can be polymerized to high conversion at room temperature, and may be facilely modified to yield a wide range of functional materials.

Allylic Epoxides Increase the Strain Energy of Cyclic Olefin Monomers for Ring‐Opening Metathesis Polymerization

Ring‐opening metathesis polymerization (ROMP) is an effective method for synthesizing functional polymers, but since the technique typically relies on high ring strain cyclic olefins, the most common monomers are norbornene derivatives. The reliance on one class of monomer limits the obtainable properties of ROMP polymers. In this work, we investigate new bicyclic monomers synthesized via epoxidation of commercial dienes. DFT estimates of these monomers’ ring strains suggests a significant increase in strain for cyclic olefins containing allylic epoxides. We found that the eight‐membered (3,4‐COO) and five‐membered (CPO) cyclic olefins were particularly effective for ROMP. CPO was of especially intriguing due to its excellent polymerizability when compared to the limited reactivity of other five‐membered rings. Unlike polynorbornenes, the resulting polymers of both monomers displayed glass transition temperatures well below room temperature. Interestingly, poly(3,4‐COO) showed both high stereo‐ and regioregularity while poly(CPO) showed little regularity. Both polymers could be readily modified via post‐polymerization ring‐opening of the reactive allylic epoxides. With a high epoxide density in poly(CPO), CPO is an exciting new ROMP monomer that is easily synthesized, can be polymerized to high conversion at room temperature, and may be facilely modified to yield a wide range of functional materials.