Search results for: epoxides

Authors: Tzu-Wen Liu, Yi-Feng Lin, Yu-Shao Chen

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CO_2 is believed to be partly responsible for changes to the global climates. Carbon capture and storage (CCS) is one way to reduce carbon dioxide emissions in the past. Recently, how to convert the captured CO_2 into fine chemicals gets lots of attention owing to reducing carbon dioxide emissions and providing greener feedstock for the chemicals industry. A variety of products can be manufactured from carbon dioxide and the most attractive products are cyclic carbonates. Therefore, the kind of catalyst plays an important role in cycloaddition of carbon dioxide to epoxides. Magnesium oxide can be an efficiency heterogeneous catalyst for the cycloaddition of carbon dioxide to epoxides because magnesium oxide has both acid and base active sites and can provide the adsorption of carbon dioxide, promoting ring-opening reaction. Spinning disk reactor (SDR) is one of the device of high-gravity technique and has successfully used for synthesis of nanoparticles by precipitation methods because of the high mass transfer rate. Synthesis of nanoparticles in SDR has advantages of low energy consumption and easy to scale up. The aim of this research is to synthesize magnesium hydroxide nanoparticles in SDR as precursors for magnesium oxide. Experimental results showed that the calcination temperature of magnesium hydroxide to magnesium oxide, and the pressure and temperature of cycloaddition reaction had significantly effect on the conversion and selectivity of the reaction.

Keywords: magnesium oxide, catalyst, cycloaddition, spinning disk reactor, carbon dioxide

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Authors: G. Imran, A. Pandurangan

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Epoxides constitute important intermediates for the production of fine and bulk chemicals as well as valuable building blocks for the synthesis of a variety of bioactive molecules. Manganese oxides are used as selective catalyst for various redox type reactions and also effectively used in the field of catalytic disposal of pollutants. Non-toxic, cost efficient factor and more over existence of wide range of oxidation state (+2 to +7) makes catalyst more interesting for both academic research and industrial applications. However, the serious drawback lying is the lower surface area. Exceedingly dispersed manganese oxide grafted over mesoporous solid material KIT-6 through ALD (Atomic Layer Deposition) technique effectively catalyze cyclohexene with H2O2 (30% in water) to corresponding epoxides. Highly selective epoxide >99% with 55.7% conversion of cyclohexene was achieved using huge dispersed active sites of MnOx species containing catalysts. Various weight percent such as (1, 3, 5, 7 & 10 wt %) of manganese (II) acetylacetonate complex was employed as Mn source to post-graft via active silanol groups of KIT-6 and are designated as (Mn-G-KIT-6). XRD, N2 sorption, HR-TEM, DRS-UV-VIS, EPR and H2-TPR were employed for structural and textural properties. Immense Mn species of about 95% proportion on silica matrix obtained was evident from ICP-OES.The resulting materials exhibited Type IV adsorption isotherms indiacting mesopore in nanorange. Si-KIT-6 and Mn-G-KIT-6 materials exhibited surface area of 519-289 m2/g and with decrease in pore volume of 0.96-0.49 cm3/g with pore diameter ranging 7.9- 7.2 with increase in wt%. DRS-UV-VIS spectroscopy and EPR studies reveal that manganese coexists as Mn2+/3+ species as extra-framework sites and frame-work sites that result in dispersion on surface of silica matrix of KIT-6 and incorporated manganese sites with silanol groups along with small sized MnO cluster, evident from HR-TEM which increase with Mn content. Conventional production of epoxides by the intramolecular etherification of chlorohydrins formed by the reaction of alkenes with hypochlorous acid is the major drawbacks obtained recently. The most efficient synthesis of oxiranes (epoxides) is obtained by mesoporous catalysts (Mn-G-KIT-6) are presented here and discussed.

Keywords: ALD, epoxidation, mesoporous, MnOx

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Authors: Ujjawal Kumar Bhagat, Kamaluddin, Rama Krishna Peddinti

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The Huisgen’s 1,3-dipolar [3+2] cycloaddition of organic azides and alkynes often give the mixtures of both the regioisomers 1,4- and 1,5- disubstituted 1,2,3-triazoles. Later, in presence of metal salts (click chemistry) such as copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC) was used for the synthesis of 1,4-disubstituted 1,2,3-triazoles as a sole products regioselectively. Also, the ‘click reactions’ of Ruthenium-catalyzed azides-alkynes cycloaddition (RuAAC) is used for the synthesis of 1,5-disubstituted 1,2,3-triazoles as a single isomer. The synthesis of 1,4- and 1.5-disubstituted 1,2,3-triazoles has become the gold standard of ‘click chemistry’ due to its reliability, specificity, and biocompatibility. The 1,4- and 1,5-disubstituted 1,2,3-triazoles have emerged as one of the most powerful entities in the varieties of biological properties like antibacterial, antitubercular, antitumor, antifungal and antiprotozoal activities. Some of the 1,4,5-trisubstituted 1,2,3-triazoles exhibit Hsp90 inhibiting properties. The 1,4-disubstituted 1,2,3-triazoles also play a big role in the area of material sciences. The triazole-derived oligomeric, polymeric structures are the potential materials for the preparation of organic optoelectronics, silicon elastomers and unimolecular block copolymers. By the virtue of hydrogen bonding and dipole interactions, the 1,2,3-triazole moiety readily associates with the biological targets. Since, the 4-aryl-1H-1,2,3-triazoles are stable entities, they are chemically robust and very less reactive. In this regard, the addition of 4-aryl-1H-1,2,3-triazoles as nucleophiles to α,β-unsaturated carbonyls and nucleophilic substitution with the epoxides constitutes a powerful and challenging synthetic approach for the generation of disubstituted 1,2,3-triazoles. Herein, we have developed aza-Michael addition of 4-aryl-1H-1,2,3-triazoles to 2-cycloalken-1-ones in the presence of an organic base (DABCO) in acetonotrile solvent leading to the formation of disubstituted 1,2,3-triazoles. The reaction provides 1,4-disubstituted triazoles, 3-(4-aryl-1H-1,2,3-triazol-1-yl)cycloalkanones in major amount along with 1,5-disubstituted 1,2,3-triazoles, minor regioisomers with excellent combined chemical yields (upto99%). The nucleophilic behavior of 4-aryl-1H-1,2,3-triazoles was also tested in the ring opening of meso-epoxides in the presence of organic bases (DABCO/Et3N) in acetonotrile solvent furnishing the two regioisomers1,4- and 1,5-disubstituted 1,2,3-triazoles. Thus, the novelty of this methodology is synthesis of diversified disubstituted 1,2,3-triazoles under metal free condition.The results will be presented in detail.

Keywords: aza-Michael addition, cycloalkenones, epoxides, triazoles

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Authors: M. Abdoul-Hakim, a. Zeroual, H. Garmes

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In a route for the preparation of 1,4-benzoxazepine fused to benzimidazole, the use of 2-(2-methoxyphenyl)-benzimidazole or styrene-derived N-tosylaziridine does not give the desired products. On this basis, we theoretically studied this reaction using DFT at the B3LYP/6-31+G(d) level. The analysis of the results shows a preferential nucleophilic attack of 2-(2-fluorophenyl)-benzimidazole on the terminal carbon atom of the Alkylepoxides and on the substituted carbon of N-tosylaziridine. Taking into account the solvent effect (DMF) makes the reactions spontaneous for the opening of epoxides and N-tosylaziridine and disfavors the intramolecularnucleophilic aromatic substitution reaction step of the products of the attack of 2-(2-methoxyphenyl)benzimidazole on an epoxide and those of the opening of N-tosylaziridine, which is consistent with the experiment.

Keywords: alkylepoxides, 4-benzoxazepine fused to benzimidazole imine, benzonitrile N-oxide, DFT, intramolecular nucleophilic aromatic substitution, N-tosyl aziridine

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Authors: Gabriel S. De Oliveira, Patricia P. Adriani, Christophe Moriseau, Bruce D. Hammock, Felipe S. Chambergo

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Epoxide hydrolases (EHs) are enzymes that are present in all living organisms and catalyze the hydrolysis of epoxides to the corresponding vicinal diols. EHs have high biotechnological interest for the drug design and chemistry transformation for industries. In this study, we describe the identification of substrates and inhibitors of epoxide hydrolase enzyme from the filamentous fungus Trichoderma reesei (TrEH), and these inhibitors showed the fungal growth inhibitory activity. We have used the cloned enzyme and expressed in E. coli to develop the screening in the library of fluorescent substrates with the objective of finding the best substrate to be used in the identification of good inhibitors for the enzyme TrEH. The substrate (3-phenyloxiranyl)-acetic acid cyano-(6-methoxy-naphthalen-2-yl)-methyl ester showed the highest specific activity and was chosen for the next steps of the study. The inhibitors screening was performed in the library with more than three thousand molecules and we could identify the 6 best inhibitors. The IC50 of these molecules were determined in nM and all the best inhibitors have urea or amide in their structure, because It has been recognized that these groups fit well in the hydrolase catalytic pocket of the epoxide hydrolases. Then the growth of T. reesei in PDA medium containing these TrEH inhibitors was tested, and fungal growth inhibition activity was demonstrated with more than 60% of inhibition of fungus growth in the assay with the TrEH inhibitor with the lowest IC50. Understanding how this EH enzyme from T. reesei responds to inhibitors may contribute for the study of fungal metabolism and drug design against pathogenic fungi.

Keywords: epoxide hydrolases, fungal growth inhibition, inhibitor, Trichoderma reesei

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Authors: Zahra Dehghani, Hoda Dehghani, Elham Zarenezhad

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1,2,3-Triazole derivatives are important compounds in medicinal chemistry owing to their wide applications in drug discovery. They can readily associate with biologically targets through the hydrogen bonding and dipole interactions. The 1,2,3-triazole core is a key structural motif in many bioactive compounds, exhibiting a broad spectrum of biological activities, such as antiviral, anticancer, anti-HIV, antibiotic, antibacterial, and antimicrobial. Additionally, they have found significant industrial applications as dyes, agrochemicals, corrosion inhibitors, photo stabilizers, and photographic materials. we disclose the synthesis and characterization of 1-azido-3-(aryl-2-yloxy)propan-2-ol drivatives. The chemistry works well with various ß-azido alcohols involving aryloxy, alkoxy and alkyl residues, and also tolerates a wide spectrum of electron-donating and electron-withdrawing functional groups in both alkyne and azide molecules. Most of ß-azidoalcohols used in these experiments were pre-synthesized by the regioselective ring opening reaction of corresponded epoxides with sodium azide, whereas the majority of terminal alkynes were prepared via SN2-type reaction of propargyl bromide and corresponded nucleophiles. To evaluate the bioactivity of title compounds, the in vitro antifungal activity of all compound was investigated against several pathogenic fungi including Candida albicans, Candida krusei, Aspergillus niger, and Trichophyton rubrum , clotrimazole and fluconazole was used as standard antifungal drugs, also To understand the antibacterial activity of synthesized compounds, they were in vitro screened against E. coli and S. aureus as Gram-negative and Gram-positive bacteria, respectively. The in vitro tests have shown the promising antifungal but marginal antibacterial activity against tested fungi and bacteria.

Keywords: biological activities, antibacterial, antifungal, 1, 2, 3-Triazole

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Authors: Caroline Rocco, Feyza Karasu, Céline Croutxé-Barghorn, Xavier Allonas, Maxime Lecompère, Gérard Riess, Yujing Zhang, Catarina Esteves, Leendert van der Ven, Rolf van Benthem Gijsbertus de With

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Acrylates are widely used in UV-curing technology. Their high reactivity can, however, limit their conversion due to early vitrification. In addition, the free radical photopolymerization is known to be sensitive to oxygen inhibition leading to tacky surfaces. Although epoxides can lead to full polymerization, they are sensitive to humidity and exhibit low polymerization rate. To overcome the intrinsic limitations of both classes of monomers, Interpenetrating Polymer Networks (IPNs) can be synthesized. They consist of at least two cross linked polymers which are permanently entangled. They can be achieved under thermal and/or light induced polymerization in one or two steps approach. IPNs can display homogeneous to heterogeneous morphologies with various degrees of phase separation strongly linked to the monomer miscibility and also synthesis parameters. In this presentation, we synthesize UV-cured methacrylate - epoxide based IPNs with different chemical compositions in order to get a better understanding of their formation and phase separation. Miscibility before and during the photopolymerization, reaction kinetics, as well as mechanical properties and morphology have been investigated. The key parameters controlling the morphology and the phase separation, namely monomer miscibility and synthesis parameters have been identified. By monitoring the stiffness changes on the film surface, atomic force acoustic microscopy (AFAM) gave, in conjunction with polymerization kinetic profiles and thermomechanical properties, explanations and corroborated the miscibility predictions. When varying the methacrylate / epoxide ratio, it was possible to move from a miscible and highly-interpenetrated IPN to a totally immiscible and phase-separated one.

Keywords: investigation of properties and morphology, kinetics, phase separation, UV-cured IPNs

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Authors: Agnieszka Feliczak-Guzik, Paulina Szczyglewska, Izabela Nowak

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A catalyst-assisted oxidation reaction is one of the key reactions exploited by various industries. Their conductivity yields essential compounds and intermediates, such as alcohols, epoxides, aldehydes, ketones, and organic acids. Researchers are devoting more and more attention to developing active and selective materials that find application in many catalytic reactions, such as cyclohexene epoxidation. This reaction yields 1,2-epoxycyclohexane and 1,2-diols as the main products. These compounds are widely used as intermediates in the perfume industry and synthesizing drugs and lubricants. Hence, our research aimed to use hierarchical zeolites modified with transition metal ions, e.g., Nb, V, and Ta, in the epoxidation reaction of cyclohexene using microwaveheating. Hierarchical zeolites are materials with secondary porosity, mainly in the mesoporous range, compared to microporous zeolites. In the course of the research, materials based on two commercial zeolites, with Faujasite (FAU) and Zeolite Socony Mobil-5 (ZSM-5) structures, were synthesized and characterized by various techniques, such as X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), and low-temperature nitrogen adsorption/desorption isotherms. The materials obtained were then used in a cyclohexene epoxidation reaction, which was carried out as follows: catalyst (0.02 g), cyclohexene (0.1 cm3), acetonitrile (5 cm3) and dihydrogen peroxide (0.085 cm3) were placed in a suitable glass reaction vessel with a magnetic stirrer inside in a microwave reactor. Reactions were carried out at 45° C for 6 h (samples were taken every 1 h). The reaction mixtures were filtered to separate the liquid products from the solid catalyst and then transferred to 1.5 cm3 vials for chromatographic analysis. The test techniques confirmed the acquisition of additional secondary porosity while preserving the structure of the commercial zeolite (XRD and low-temperature nitrogen adsorption/desorption isotherms). The results of the activity of the hierarchical catalyst modified with niobium in the cyclohexene epoxidation reaction indicate that the conversion of cyclohexene, after 6 h of running the process, is about 70%. As the main product of the reaction, 2-cyclohexanediol was obtained (selectivity > 80%). In addition to the mentioned product, adipic acid, cyclohexanol, cyclohex-2-en-1-one, and 1,2-epoxycyclohexane were also obtained. Furthermore, in a blank test, no cyclohexene conversion was obtained after 6 h of reaction. Acknowledgments The work was carried out within the project “Advanced biocomposites for tomorrow’s economy BIOG-NET,” funded by the Foundation for Polish Science from the European Regional Development Fund (POIR.04.04.00-00-1792/18-00.

Keywords: epoxidation, oxidation reactions, hierarchical zeolites, synthesis

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Authors: Matthew E. Potter, Daniel J. Stewart, Lindsay M. Armstrong, Pier J. A. Sazio, Robert R. Raja

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Rising CO₂ levels in the atmosphere means that CO₂ is a highly desirable feedstock. This requires specific catalysts to be designed to activate this inert molecule, combining a catalytic site tailored for CO₂ transformations with a support that can readily adsorb CO₂. Metal organic frameworks (MOFs) are regularly used as CO₂ sorbents. The organic nature of the linker molecules, connecting the metal nodes, offers many post-synthesis modifications to introduce catalytic active sites into the frameworks. However, the metal nodes may be coordinatively unsaturated, allowing them to bind to organic moieties. Imidazoles have shown promise catalyzing the formation of cyclic carbonates from epoxides with CO₂. Typically, this synthesis route employs toxic reagents such as phosgene, liberating HCl. Therefore an alternative route with CO₂ is highly appealing. In this work we design active sites for CO₂ activation, by tethering substituted-imidazole organocatalytic species to the available Cr3+ metal nodes of a Cr-MIL-101 MOF, for the first time, to create a tailored species for carbon capture utilization applications. Our tailored design strategy combining a CO₂ sorbent, Cr-MIL-101, with an anchored imidazole results in a highly active and selective multifunctional catalyst, achieving turnover frequencies of over 750 hr-1. These findings demonstrate the synergy between the MOF framework and imidazoles for CO₂ utilization applications. Further, the effect of substrate variation has been explored yielding mechanistic insights into this process. Through characterization, we show that the structural and compositional integrity of the Cr-MIL-101 has been preserved on functionalizing the imidazoles. Further, we show the binding of the imidazoles to the Cr3+ metal nodes. This can be seen through our EPR study, where the distortion of the Cr3+ on binding to the imidazole shows the CO₂ binding site is close to the active imidazole. This has a synergistic effect, improving catalytic performance. We believe the combination of MOF support and organocatalyst allows many possibilities to generate new multifunctional catalysts for CO₂ utilisation. In conclusion, we have validated our design procedure, combining a known CO₂ sorbent, with an active imidazole species to create a unique tailored multifunctional catalyst for CO₂ utilization. This species achieves high activity and selectivity for the formation of cyclic carbonates and offers a sustainable alternative to traditional synthesis methods. This work represents a unique design strategy for CO₂ utilization while offering exciting possibilities for further work in characterization, computational modelling, and post-synthesis modification.

Keywords: carbonate, catalysis, MOF, utilisation

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Authors: Khodzhaberdi Allaberdiev

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In order to understand the interactions on the interface polyamide fibers and epoxy matrix in fiber- reinforced composites were investigated industrial aramid fibers: armos, svm, terlon using individual epoxy matrix components, epoxies: diglycidyl ether of bisphenol A (DGEBA), three- and diglycidyl derivatives of m, p-amino-, m, p-oxy-, o, m,p-carboxybenzoic acids, the models: curing agent, aniline and the compound, that depict of the structure the primary addition reaction the amine to the epoxy resin, N-di (oxyethylphenoxy) aniline. The chemical structure of the surface of untreated and treated polyamide fibers analyzed using Fourier transform infrared spectroscopy (FTIR). The impregnation of fibers with epoxy matrix components and N-di (oxyethylphenoxy) aniline has been carried out by heating 150˚C (6h). The optimum fiber loading is at 65%.The result a thermal treatment is the covalent bonds formation , derived from a combined of homopolymerization and crosslinking mechanisms in the interfacial region between the epoxy resin and the surface of fibers. The reactivity of epoxy resins on interface in microcomposites (MC) also depends from processing aids treated on surface of fiber and the absorbance moisture. The influences these factors as evidenced by the conversion of epoxy groups values in impregnated with DGEBA of the terlons: industrial, dried (in vacuum) and purified samples: 5.20 %, 4.65% and 14.10%, respectively. The same tendency for svm and armos fibers is observed. The changes in surface composition of these MC were monitored by X-ray photoelectron spectroscopy (XPS). In the case of the purified fibers, functional groups of fibers act as well as a catalyst and curing agent of epoxy resin. It is found that the value of the epoxy groups conversion for reinforced formulations depends on aromatic polyamides nature and decreases in the order: armos >svm> terlon. This difference is due of the structural characteristics of fibers. The interfacial interactions also examined between polyglycidyl esters substituted benzoic acids and polyamide fibers in the MC. It is found that on interfacial interactions these systems influences as well as the structure and the isomerism of epoxides. The IR-spectrum impregnated fibers with aniline showed that the polyamide fibers appreciably with aniline do not react. FTIR results of treated fibers with N-di (oxyethylphenoxy) aniline fibers revealed dramatically changes IR-characteristic of the OH groups of the amino alcohol. These observations indicated hydrogen bondings and covalent interactions between amino alcohol and functional groups of fibers. This result also confirms appearance of the exo peak on Differential Scanning Calorimetry (DSC) curve of the MC. Finally, the theoretical evaluation non-covalent interactions between individual epoxy matrix components and fibers has been performed using the benzanilide and its derivative contaning the benzimidazole moiety as a models of terlon and svm,armos, respectively. Quantum-topological analysis also demonstrated the existence hydrogen bond between amide group of models and epoxy matrix components.All the results indicated that on the interface polyamide fibers and epoxy matrix exist not only covalent, but and non-covalent the interactions during the preparation of MC.

Keywords: epoxies, interface, modeling, polyamide fibers

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