- Synthesis of cyclic carbonates from carbon dioxide and epoxides catalyzed by a keggin-type polyoxometalate-supported rhenium carbonyl derivate in ionic liquid
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A monovacant Keggin-type polyoxometalate-supported trirhenium carbonyl derivate [(CH3)4N]5H23[(PW11O39){Re(CO)3}3(μ3-O)(μ2-OH)]4·24H2O was synthesized. It was used as a catalyst for the synthesis of cyclic carbonates from carbon dioxide and epoxides under mild reaction conditions with co-catalyst pyrrolidinium bromide. The catalyst system was recycled 10 times with only a small decline in yield. The catalytic mechanism was hypothesized based on experimental results and the frontier orbitals computed by DFT calculations.
- Huo, Zhiyuan,Zhao, Juan,Bu, Zhanwei,Ma, Pengtao,Liu, Qisen,Niu, Jingyang,Wang, Jingping
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- Triazine-based Organic Polymer-catalysed Conversion of Epoxide to Cyclic Carbonate under Ambient CO2 Pressure
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In this work we have achieved epoxide to cyclic carbonate conversion using a metal-free polymeric catalyst under ambient CO2 pressure (1.02 atm) using a balloon setup. The triazine containing polymer (CYA-ANIS) was prepared from cyanuric chloride (CYA?Cl) and o-dianisidine (ANIS) in anhydrous DMF as solvent by refluxing under the N2 gas environment. The presence of triazine and amine functional groups in the polymer results in the adsorption of CO2 up to 7 cc/g at 273 K. This inspired us to utilize the polymer for the conversion of a series of functionalised epoxides into their corresponding cyclic carbonates in the presence of tetrabutyl ammonium iodide (TBAI) as co-catalyst. The product has wide range of applications like solvent in lithium ion battery, precursor for polycarbonate, etc. The catalyst was efficient for the conversion of different mono and di-epoxides into their corresponding cyclic carbonates under atmospheric pressure in the presence of TBAI as co-catalyst. The study indicates that epoxide attached with electron withdrawing groups (like, CH2Cl, glycidyl ether, etc.) displayed better conversion compared to simple alkane chain attached epoxides. This is mainly due to the stabilization of electron rich intermediates produced during the reaction (e. g. epoxide ring opening or CO2 incorporation into the halo-alkoxide anion). This catalyst mixture was capable to maintain its reactivity up to five cycles without losing its activity. Post catalytic characterization clearly supports the heterogeneous and recyclable nature of the catalyst.
- Biswas, Tanmoy,Halder, Arjun,Paliwal, Khusboo S.,Mitra, Antarip,Tudu, Gouri,Banerjee, Rahul,Mahalingam, Venkataramanan
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- New iron pyridylamino-bis(Phenolate) catalyst for converting CO2 into cyclic carbonates and cross-linked polycarbonates
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The atom-efficient reaction of CO2 with a variety of epoxides has been efficiently achieved employing iron pyridylamino-bis(phenolate) complexes as bifunctional catalysts. The addition of a Lewis base co-catalyst allowed significant reduction in the amount of iron complex needed to achieve high epoxide conversions. The possibility of controlling the selectivity of the reaction towards either cyclic carbonate or polycarbonate was evaluated. An efficient switch in selectivity could be achieved when cyclic epoxides such as cyclohexene oxide and the seldom explored 1,2-epoxy-4-vinylcyclohexane were used as substrates. The obtained poly(vinylcyclohexene carbonate) presents pending vinyl groups, which allowed post-synthetic cross-linking by reaction with 1,3-propanedithiol. The cross-linked polycarbonate displayed a substantial increase in the glass transition temperature and chemical resistance, thus opening new opportunities for the application of these green polymers. CO2 meets epoxides: Iron pyridylamino-bis(phenolate) complexes are highly active catalysts for the atom-efficient reaction of CO2 with a variety of epoxides. The selectivity can be switched between the cyclic or polymeric carbonate when using cyclic epoxides such as cyclohexene oxide and 1,2-epoxy-4-vinylcyclohexaneas substrates. Cross-linking of the obtained poly(vinylcyclohexene carbonate) leads to substantial increase in the Tg and chemical resistance of the polymer.
- Taherimehr, Masoumeh,Sert?, Jo?o Paulo Cardoso Costa,Kleij, Arjan W.,Whiteoak, Christopher J.,Pescarmona, Paolo P.
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- Anion-induced 3d-4f luminescent coordination clusters: Structural characteristics and chemical fixation of CO2 under mild conditions
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Two series of anion-induced 3d-4f luminescent clusters ZnII2LnIII2L4 (LnIII = Eu3+, Tb3+, Er3+, Yb3+, Nd3+) and ZnII4LnIII2L4 (LnIII = Tb3+, Nd3+) based on μ3-OH group were synthesized and characterized. The difference in anions not only leads to significant structural changes, but also changes the luminescent properties of the 3d-4f coordination clusters. These complexes show excellent catalytic performance for CO2 conversion to obtain cyclic carbonates with wide substrate scopes and high selectivity under mild conditions. Turnover numbers were up to 9000, and turnover frequencies obtained were 660 h-1. The ligand is simple and the complexes are easily obtained even on a large scale. Moreover, these complexes also feature lanthanide-characterized luminescence both in visible and near infrared regions with relatively long luminescence lifetimes and high quantum yields, suggesting promising multifunctional applications.
- Zhang, Ruilian,Wang, Li,Xu, Cong,Yang, Huan,Chen, Wanmin,Gao, Guoshu,Liu, Weisheng
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- Bifunctional one-component catalysts for the addition of carbon dioxide to epoxides
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Several bifunctional ammonium salts were synthesized and employed as one-component catalysts for the conversion of CO2 and epoxides to produce cyclic carbonates. These catalysts show superior activities compared to their monofunctional analogs. A turnover number of up to 693 and a turnover frequency of up 392h-1 could be achieved for the best catalyst. Moreover, the effect of various solvents has been studied. All employed solvents and the product formed had a negative influence on substrate conversion. The scope and limitation of the reaction has been studied carefully for two general reaction protocols at 45 and 90-°C. In over 20 examples, the isolated yields after filtration were 90-%. In addition, we present the first organocatalyzed synthesis of a cyclohexene-based naturally occurring cyclic carbonate, and its molecular structure was determined by XRD. Furthermore, we demonstrate that the reaction can be performed even on a multigram scale and can be monitored by insitu FTIR spectroscopy. Couple up: Recyclable bifunctional ammonium salts are identified as one-component catalysts for the 100-% atom-economic coupling reaction of CO2 and epoxides even at 45-°C. The alcohol moiety that donates a hydrogen bond accelerates the catalytic reaction remarkably. This metal and solvent-free process can be performed on a multigram scale and is applied to the synthesis of a naturally occurring cyclic carbonate.
- Büttner, Hendrik,Lau, Kornelia,Spannenberg, Anke,Werner, Thomas
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- Simultaneous shaping and confinement of metal-organic polyhedra in alginate-SiO2spheres
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The simultaneous shaping and confinement of Cu-based MOP in alginate-SiO2 spheres significantly enhance the mechanical strength and leaching resistance of Cu-MOP. The resulting MOP-alginate-SiO2 is shown through chemical fixation of CO2 to exhibit improved product yield over the parent Cu-MOP and Cu-alginate-SiO2. This journal is
- Zhang, Zhuxiu,Lei, Yifan,Zhou, Jie,Cui, Mifen,Chen, Xian,Fei, Zhaoyang,Liu, Qing,Tang, Jihai,Qiao, Xu
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- Transparent, flexible and highly conductive ion gels from ionic liquid compatible cyclic carbonate network
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Transparent, flexible, self-standing and highly ion conductive ion gels have been synthesised from novel ionic liquid compatible cyclic carbonate (CC) network polymer. The use of dual functional cyclic carbonate methacrylate (CCMA) monomer for the synthes
- Jana, Satyasankar,Parthiban, Anbanandam,Chai, Christina L. L.
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- Highly Efficient Polymer-Supported Catalytic System for the Valorization of Carbon Dioxide
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Polydibenzo-18-crown-6 was utilized as a co-catalyst and polymeric support in combination with potassium iodide for the synthesis of cyclic carbonates from carbon dioxide and epoxides under mild and solvent-free conditions. The efficiency of this catalytic system can be easily increased by loading the polymer with KI prior to the reaction. The influence of various reaction parameters were studied thoroughly. The scope and limitation of the catalyst system was studied at 80 °C and 100 °C. A large number of terminal epoxides (14) were converted to the desired cyclic carbonates in yields up to 99 %. We could successfully recover and reuse the catalyst >20 times with excellent yields up to 99 %. Although, we observed that the activity gradually decreased after repetitive cycles. This decrease was attributed to KI leaching and partial degradation caused by mechanical stirring. This assumption is supported by scanning electron microscopy and energy dispersive X-ray spectroscopy.
- Desens, Willi,Kohrt, Christina,Frank, Marcus,Werner, Thomas
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- Synthesis of bifunctional cyclic carbonates from CO2 catalysed by choline-based systems
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Easily prepared choline iodide is an active catalyst for the synthesis of cyclic carbonates through the coupling reaction of CO2 and epoxides using low pressure (1 MPa), moderate temperature (85 °C) and green solvents (ethanol and propan-2-ol). The effects of reaction temperature, pressure, reaction time and amount of catalyst used were also investigated. The results showed moderate to high yields and excellent selectivities of cyclic carbonates with vinyl or acrylate groups under mild reaction conditions. The heterogenization of choline over a Merrifield resin gives access to a supported catalyst with good recyclability and reactivity that can be extended to a variety of terminal epoxide substrates.
- Amaral, Adérito J.R.,Coelho, Jorge F.J.,Serra, Arménio C.
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- An Efficient and Versatile Lanthanum Heteroscorpionate Catalyst for Carbon Dioxide Fixation into Cyclic Carbonates
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A new lanthanum heteroscorpionate complex has shown exceptional catalytic activity for the synthesis of cyclic carbonates from epoxides and carbon dioxide. This catalyst system also promotes the reaction of bio-based epoxides to give an important class of bis(cyclic carbonates) that can be further used for the production of bio-derived non-isocyanate polyurethanes. The catalytic process requires low catalyst loading and mild reaction conditions for the synthesis of a wide range of cyclic carbonates.
- Martínez, Javier,Fernández-Baeza, Juan,Sánchez-Barba, Luis F.,Castro-Osma, José A.,Lara-Sánchez, Agustín,Otero, Antonio
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- Facile CO2 Cycloaddition to Epoxides by Using a Tetracarbonyl Metal Selenotungstate Derivate [{Mn(CO)3}4(Se2W11O43)]8-
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A novel polyoxometalate cluster, i.e., Na1.5H4.5[(CH3)4N]2{[Mn(CO)3]4(Se2W11O43)}·9H2O (1), has been successfully synthesized under moderately acidic conditions. Compound 1 contains four electron-donating {Mn(CO)3}+ organometallic entities, which are grafted over an unprecedented heteropolytungstate electron-acceptor group. Compound 1 was further structurally characterized by various physicochemical techniques like elemental analyses, inductively coupled plasma (ICP) analyses, IR and UV-vis spectroscopy, electrochemistry, and single-crystal X-ray diffraction, and so on. The polyoxoanion of 1 comprises a novel {Se2W11} fragment, which is obtained from molecular assembly of rare {SeW3} and {SeW8} species. Evaluation of the data from solution-state IR spectrum showed excellent agreement with the solid state IR spectrum, indicating the intact clusters in the CH3CN/Na2SO4 solvent. Also, negative electrospray ionization mass spectrometry (ESI-MS) was an alternative tool to verify the stability of 1 in the mixed solvent. Additionally, the resulting hybrid can act as a catalyst for cyclic carbonate formation from the reactants epoxides and CO2 under modest reaction conditions in conjunction with a 1-ethyl-1-methylpyrrolidinium bromide (2). The good activity can be substantiated due to the cooperative influence of polyoxoanion and Br- ions. Complex 1 can also be easily recycled and reused three times without obvious decrease of catalytic activity.
- Lu, Jingkun,Ma, Xinyi,Singh, Vikram,Zhang, Yujiao,Wang, Ping,Feng, Junwei,Ma, Pengtao,Niu, Jingyang,Wang, Jingping
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- Design and synthesis of a new magnetic metal organic framework as a versatile platform for immobilization of acidic catalysts and CO2fixation reaction
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In this study, a new magnetic metal organic framework (MNP@MOF) with a core-shell structure has been introduced as an efficient and versatile platform for immobilization of Preyssler (H14[NaP5W30O110]) heteropolyacid (PR HPA). The chemical structure of the nanocatalyst was analyzed by using different techniques, including HRTEM, TEM, HRTEM mapping, SEM, EDX, TGA, XRD, VSM, BET and ICP. These analyses confirmed the core-shell and spherical structure of the catalyst and successful immobilization of PR HPA on its surface. After complete characterization, the efficiency of the catalyst was tested for the synthesis of cyclic carbonates by the chemical fixation of carbon dioxide. Different epoxides were converted to cyclic carbonates in the presence of 0.4 mol% of catalyst and a 0.3 MPa CO2pressure under solvent-free conditions. To date, this reaction has been performed with various heterogeneous catalysts, but this is the first report on the use of PR HPA and MNP@MOF for this reaction.
- Abnous, Khalil,Khalifeh, Reza,Khojastehnezhad, Amir,Rajabzadeh, Maryam,Rezaei, Fahimeh,Taghavi, Faezeh,Taghdisi, Seyed Mohammad
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- Multifunctional and Sustainable Fe-Iminopyridine Complexes for the Synthesis of Cyclic Carbonates
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The use of multifunctional and sustainable Fe catalysts for the formation of cyclic carbonates from epoxides and carbon dioxide at 80 °C and 3 bar pressure is presented. The optimal catalyst possesses a halide counteranion and a hydrogen bond donor to activate the epoxide for ring opening, affording a single-component, cocatalyst-free catalytic system.
- Seong, Eun Young,Kim, Jae Hyung,Kim, Nam Hee,Ahn, Kwang-Hyun,Kang, Eun Joo
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- Efficient Catalysts of Acyclic Guanidinium Iodide for the Synthesis of Cyclic Carbonates from Carbon Dioxide and Epoxides under Mild Conditions
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We have studied the synthesis of five-membered cyclic carbonates through the cycloaddition of CO 2 to epoxides by using acyclic guanidinium salts. We have found that the cycloaddition reactions proceed smoothly at ordinary temperatures and pressures and result in good yields when acyclic guanidinium iodides are employed as catalysts. Both cation moiety and anion moiety of the guanidinium salts play important roles in their catalytic activity. It is essential to have active hydrogens on the cation moiety as well as an iodide ion as the anion moiety so as to achieve good catalytic activity. Guanidinium iodides with three or more active hydrogens give cyclic carbonates in high yields in polar solvents such as 1-methylpyrrolidin-2-one, whereas the guanidinium iodides with one or two active hydrogens show good catalytic activity in less polar solvents such as 2-methyltetrahydrofuran.
- Aoyagi, Naoto,Endo, Takeshi,Furusho, Yoshio
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- High conversion of CO2 into cyclic carbonates under solvent free and ambient pressure conditions by a Fe-cyanide complex
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Methods of converting carbon dioxide into valuable chemicals are of great demand but their development is still challenging. Herein, we developed an efficient, green and facile synthetic method for the preparation of a Fe-cyanide complex. The target catalyst showed high catalytic activity for the cyclic reaction of carbon dioxide and epoxide under solvent free conditions and ambient pressure. Meanwhile, the effects of morphology of different catalysts on their catalytic activities were also investigated by the kinetic and thermodynamic studies. In addition, the catalyst could be recycled and reused for at least five successive cycles without significant decrease in the catalytic activity. This target catalyst thus represents one of the efficient and recyclable systems reported for the cyclic reaction in industry.
- Jiang, Pengbo,Ma, Lei,Wang, Kaizhi,Lan, Kai,Zhan, Zhenzhen,Iqbal, Anam,Niu, Fang,Li, Rong
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- Highly efficient synthesis of cyclic carbonates from CO2 and epoxides catalyzed by KI/lecithin
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Development of efficient, cheap and non-toxic catalysts for the cycloaddition of CO2 with epoxides to produce five-membered cyclic carbonates is a very attractive topic. In this work, cycloaddition of CO 2 with propylene oxide (PO) to propylene carbonate (PC) catalyzed by potassium halides (KCl, KBr, and KI) in the presence of lecithin, which is renewable, non-toxic, environmentally benign and biocompatible, was studied. It was discovered that potassium halides and lecithin had excellent synergetic effect in promoting the reaction, and KI/lecithin catalytic system was the most efficient among them. The effects of temperature, pressure, reaction time, and amount of catalysts on the reaction were investigated using KI/lecithin as the catalyst, and the reaction conditions were optimized. At the optimal conditions, the KI/lecithin catalytic system was also very active and selective for the cycloaddition of CO2 with other epoxides, such as glycidyl phenyl ether, epichlorohydrin, styrene oxide, 1,2-epoxyhexane, and glycidyl methacrylate. The mechanism for the synergetic effect was also studied.
- Song, Jinliang,Zhang, Binbin,Zhang, Peng,Ma, Jun,Liu, Jinli,Fan, Honglei,Jiang, Tao,Han, Buxing
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- Pseudopeptidic macrocycles as cooperative minimalistic synzyme systems for the remarkable activation and conversion of CO2in the presence of the chloride anion
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A series of pseudopeptidic compounds have been assayed as organocatalyts for the conversion of CO2 into organic carbonates through a cooperative multifunctional mechanism. Conformationally constrained pseudopeptidic macrocycles 3a and 3b have been revealed to be excellent synzymes for this purpose, being able to provide a suitable preorganization of the different functional elements and reaction components to activate the CO2 molecule and stabilize the different anionic intermediates involved, through a series of cooperative supramolecular interactions. As a result, remarkable catalytic efficiencies are found at low CO2 pressures and moderate temperatures, with TON and TOF values surpassing those reported for other organocatalytic supramolecular systems under similar conditions. The process works well for monosubstituted epoxides. The involvement of the different structural elements has been analyzed in detail and preliminary studies show the potential for recovery and reuse of these catalytic systems.
- Altava, Belén,Bolte, Michael,Burguete, M. Isabel,Esteve, Ferran,García-Verdugo, Eduardo,Luis, Santiago V.
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- A chitosan derivative containing both carboxylic acid and quaternary ammonium moieties for the synthesis of cyclic carbonates
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Chitosan, a renewable feedstock, is modified and used as a catalytic support in the presence of potassium iodide. The system is highly efficient towards the incorporation of carbon dioxide (CO2) into epoxides. It demonstrates very good thermal stability and is recyclable more than five times without loss of activity. The optimal reaction conditions were determined using allylglycidyl ether as a model and extended to a wide range of other epoxides. Cyclic carbonates were obtained with very high yield in a few hours under mild conditions (2-7 bar ≈0.2-0.7 MPa, 80 °and no solvent.
- Besse, Vincent,Illy, Nicolas,David, Ghislain,Caillol, Sylvain,Boutevin, Bernard
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- Polyvinyl alcohol-potassium iodide: An efficient binary catalyst for cycloaddition of epoxides with CO2
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In this study, we have for the first time demonstrated that polyvinyl alcohol (PVA) and potassium iodide (KI) can form an efficient catalytic system for synthesis of cyclic carbonates from epoxide and CO2. The catalytic reaction happens in solvent-free conditions. A synergetic effect occur between PVA and KI which considerably increases the reaction yield. This binary catalytic system is mainly suitable for mono-substituted terminal epoxides. In the optimized reaction condition, over 90% reaction yield can be achieved. The binary catalyst is reusable and can be recycled at least five times without significant loss of the catalytic activity. The PVA hydrolysis degree affect the catalytic activity as well. A possible mechanism of synergetic effect of the binary system was proposed. PVA and KI may form a non-toxic, low cost, recyclable, highly-efficiency catalyst for fixing CO2 through cycloaddition with epoxides.
- Chang, Haibo,Li, Qingshuo,Cui, Xuemin,Wang, Hongxia,Qiao, Congzhen,Bu, Zhanwei,Lin, Tong
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- Hydroxyl-functionalized imidazoles: Highly active additives for the potassium iodide-catalyzed synthesis of 1,3-dioxolan-2-one derivatives from epoxides and carbon dioxide
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4(5)-(Hydroxymethyl)imidazole and potassium iodide were identified as an efficient catalyst system for the cycloaddition of epoxides and carbon dioxide producing 1,3-dioxolan-2-one derivatives under solvent-free conditions. The high activity of the catalyst system even at 60 C was probably due to synergistic effects between potassium iodide and the substituted imidazole. Various functionalized and nonfunctionalized terminal epoxides as well as internal epoxides were converted into the corresponding cyclic carbonates in high yields (up to 99 %) under mild reaction conditions within a short reaction time. Compared with the previously reported amino alcohols e.g. triethanolamine based catalyzed synthesis of cyclic carbonates, the catalyst system described herein demonstrates a higher activity toward a broad substrate scope A perfect combination: The combination of commercially available 4(5)-(hydroxymethyl)imidazole (HMI) and potassium iodide serves as a simple and efficient catalyst system for the coupling reaction of epoxides with carbon dioxide. Several epoxides are converted into cyclic carbonates in high yields (up to 99 %) under mild and solvent-free conditions within a short reaction time. This new catalyst system demonstrates higher activity than the previously reported potassium iodide/triethanolamine (TEA) system.
- Werner, Thomas,Tenhumberg, Nils,Büttner, Hendrik
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- Highly efficient 3d/4d-4f coordination polymer catalysts for carbon dioxide fixation into cyclic carbonates
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Two novel highly efficient 3d/4d-4f one-dimensional (1D) double-chain coordination polymer catalysts with unique structures were synthesized for the first time. An X-ray single crystal structure analysis revealed that the two compounds are isomorphous and have a 1D metal-organic network coordination polymer structure. Both compounds also showed significant thermal stability and their structures remained stable up to 325 °C. The reaction conditions, type of substrate, amount of catalyst and its catalytic mechanism were investigated. The catalysts ([Dy2M2L4 (OAc)2 (MeOH)5 (H2O)]) (M = Zn, Cd) exhibited excellent catalytic activity in the cycloaddition of CO2 and styrene oxide (C8H8O, SO). High product yields, high selectivity, and the highest turnover frequency (TOF) of 28 400 h-1 were achieved. Additionally, the catalysts can significantly enhance the application of the present types of 3d/4d-4f catalysts in catalysis for transformations involving the fixation of CO2.
- Wang, Gang,Xu, Cong,Wang, Li,Liu, Weisheng
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- Lanthanide clusters as highly efficient catalysts regarding carbon dioxide activation
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A series of tetranuclear lanthanide clusters supported by organic ligands ([Ln4L6(NO3)4]·4(MeCN), Ln = La, Nd, Sm) has been synthesized and characterized. The Lewis acidic Ln3+ sites were investigated as highly efficient catalysts regarding CO2 activation. The clusters showed significant thermal stability after 4 reaction cycles of CO2 insertion into epoxides to form cyclic carbonates, with TOF up to 6700 h-1. The catalytic system also displays a wide substrate scope and high catalytic activity. Unfortunately, the catalytic efficiency of the catalysts for some sterically hindered reaction substrates is not very satisfactory.
- Hou, Wei,Wang, Gang,Wu, Xiaojing,Sun, Shuoyi,Zhao, Chunyang,Liu, Wei-Sheng,Pan, Fuxing
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- A nona-vacant Keggin-type tricarbonyl rhenium derivative {[PMo3O16][Re(CO)3]4}5- and its catalytic performance for CO2 cycloaddition reactions
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A nona-vacant Keggin-type tricarbonyl rhenium derivative [(NH4)5]{[PMo3O16][Re(CO)3]4}·1.5H2O was obtained and characterized. Its frontier orbitals were computed by density functional theory (DFT) calculations. Furthermore, it could act as a Lewis acid catalyst and promote the conversion of CO2 to cyclic carbonate under mild reaction conditions with pyrrolidinium bromide as a co-catalyst.
- Huo, Zhiyuan,Guo, Jipeng,Lu, Jingkun,Xu, Qiaofei,Ma, Pengtao,Zhao, Juan,Zhang, Dongdi,Niu, Jingyang,Wang, Jingping
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- Synthesis of cyclic carbonates from epoxides and carbon dioxide catalyzed by MgCl2
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Magnesium chloride (MgCl2), a stable and cheap salt, works as an active catalyst for the synthesis of cyclic carbonates from epoxides and atmospheric-pressure carbon dioxide (CO2). Various epoxides are converted to the corresponding cyclic carbonates in good to high yields.
- Fujihara, Tetsuaki,Inokuchi, Masaki,Mizoe, Taiga,Nogi, Keisuke,Terao, Jun,Tsuji, Yasushi
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- A tricarbonyl rhenium(I) complex with a pendant pyrrolidinium moiety as a robust and recyclable catalyst for chemical fixation of carbon dioxide in ionic liquid
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A novel Re(I) complex covalently anchored with a pyrrolidinium moiety was successfully synthesized and used as an efficient and recyclable catalyst in the cycloaddition of CO2 with epoxides under mild reaction conditions to give excellent isolated yield and selectivity of cyclic carbonates in pyrrolidinium ionic liquid. The Royal Society of Chemistry.
- Wong, Wing-Leung,Cheung, Kwong-Chak,Chan, Pak-Ho,Zhou, Zhong-Yuan,Lee, Kam-Han,Wong, Kwok-Yin
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- Development of pyridine based: O -aminophenolate zinc complexes as structurally tunable catalysts for CO2 fixation into cyclic carbonates
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Zinc complexes of ZnLAPIPX (L = 2,4-di-tert-butyl-6-(((E)-2-(((E)-pyridin-2-lmethylene)amino)benzylidene)amino)phenol) bearing different axial ligands (X = OAc, Cl, Br, I) have been successfully synthesized and characterized. It is evident from X-ray crystallography analysis that ZnLAPIPX exists as a distorted square-pyramid in which ZnII is coordinated by an o-aminophenolate-based ligand and an X moiety in the axial position. These easily synthesized complexes have been shown to perform as effective catalysts for the coupling of epoxides and carbon dioxide to generate cyclic carbonates. Their axial ligand was found to play an important role in enhancing their catalytic activity. The ZnLAPIPI complex represents a versatile bifunctional catalyst due to the synergistic effect of both an electrophilic zinc ion and a nucleophilic iodide in one molecule to achieve a high-yield of cyclic carbonates, while ZnLAPIPOAc in cooperation with a co-catalyst affords a productive system for this coupling reaction. The effects of reaction variables such as temperature, time and pressure were systematically investigated. This solvent free route is relevant to the context of green chemistry as it provides an atom-efficient protocol for the conversion of CO2 into valuable cyclic carbonates.
- Alaji,Safaei,Wojtczak
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- Remarkably efficient catalysts of amidine hydroiodides for the synthesis of cyclic carbonates from carbon dioxide and epoxides under mild conditions
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Hydroiodides of amidines effectively catalyzed the reaction of CO 2 and epoxides under mild conditions such as ordinary pressure and ambient temperature, and the corresponding 5-membered cyclic carbonates were obtained in moderate to high yields.
- Aoyagi, Naoto,Furusho, Yoshio,Endo, Takeshi
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- A Monomeric Tricobalt(II)-Substituted Dawson-Type Polyoxometalate Decorated by a Metal Carbonyl Group: [P2W15O56Co3(H2O)3(OH)3Mn(CO)3]8-
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A monomeric tricobalt(II)-substituted phosphotungstate polyanion, [H9P2W15O62Co3]9-, is stabilized by the attachement of an organometallic group, {Mn(CO)3}, for the first time. The resulting polyoxometalate-supported [Mn(CO)3]+ complex (1) can be used as an efficient catalyst in the cycloaddition of CO2 with epoxides under mild reaction conditions with pyrrolidinium bromide as a cocatalyst. Besides, magnetic measurements show that the compound exhibits weaker ferromagnetic interactions at low temperature.
- Jia, Jiage,Niu, Yanjun,Zhang, Panpan,Zhang, Dongdi,Ma, Pengtao,Zhang, Chao,Niu, Jingyang,Wang, Jingping
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- Cyclic carbonate formation from carbon dioxide and oxiranes in tetrabutylammonium halides as solvents and catalysts
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(Matrix presented) Epoxides dissolved in molten tetralkylammonium salts bearing halides as counterions are converted into cyclic carbonates under atmospheric pressure of carbon dioxide. The reaction rate depends on the nucleophilicity of the halide ion as well as the structure of the cation.
- Calo, Vincenzo,Nacci, Angelo,Monopoli, Antonio,Fanizzi, Antonello
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- Controlled synthesis and functionalization of PEGylated methacrylates bearing cyclic carbonate pendant groups
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Homopolymer bearing cyclic carbonate (CC) group, ABA type triblock copolymers, and (AC)B(AC) type terpolymers with statistical arrangement of A and C monomers bearing side chain CC groups are reported here. Difunctional poly(ethylene glycol) macroinitiators (PEGMIs) were prepared from PEG of three different molecular weights. PEGMIs were subsequently used for the preparation of polymers bearing CC pendant groups from cyclic carbonate methacrylate (CCMA) under atom transfer radical polymerization to yield polymers with low polydispersity index. Homopolymer and ABA type triblock copolymers were obtained by polymerizing CCMA monomer and (AC)B(AC) type statistical terpolymers were obtained when methyl methacrylate was included as a comonomer. No polymer was obtained when styrene was used as comonomer. The cyclic carbonate groups were subjected to ring-opening reaction with monoamine to yield side chain hydroxyurethane polymers with increased solubility and diamines to yield crosslinked insoluble materials. Changes in wettability characteristics were studied by following the water contact angle of the polymers before and after ring-opening reaction involving the cyclic carbonate pendant group. The polymers which composed of electrolyte in the form of PEG and coordinating species in the form of pendant cyclic carbonate groups showed conductivity in the range of 2-5 × 10-6 Scm-1 at 23 °C after doping with lithium bis(trifluoromethane) sulfonimide as characterized by impedance spectroscopy.
- Jana, Satyasankar,Yu, Han,Parthiban, Anbanandam,Chai, Christina L.L.
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- Succinimide-KI: An efficient binary catalyst system for mild, solvent-free cycloaddition of CO2 to epoxides
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In this study, we have for the first time demonstrated that succinimide (SI)-KI is an efficient catalyst system to synthesize propylene carbonate (PC) from carbon dioxide (CO2) and propylene oxide (PO) at a solvent-free condition. A synergistic effect was observed between SI and KI that largely increased the reaction yield. It enabled the cycloaddition reaction to take place at 70 °C under a low pressure (0.4 MPa) for only 4 h, with a PC yield as high as 97.5%. The overall condition is milder than the reaction catalyzed by most of the other KI involved co-catalyst systems reported in literatures. The excellent catalytic ability was explained by the increased KI solubility in PO due to the presence of SI and the weak acidity of NH in SI which can be enhanced by KI. A reaction mechanism was proposed based on a reaction kinetics study. SI-KI was applicable to cycloaddition of CO2 with other epoxides. It may offer an inexpensive, environmentally-friendly route to synthesis of propylene carbonate from CO2.
- Li, Qingshuo,Chang, Haibo,Li, Runming,Wang, Hongxia,Liu, Jichun,Liu, Shanhu,Qiao, Congzhen,Lin, Tong
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- Self-assembly of tetranuclear 3d-4f helicates as highly efficient catalysts for CO2cycloaddition reactions under mild conditions
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A series of novel asymmetry 3d-4f helicates Zn3LnL4 (H2L = N-(2-((3,5-di-tert-butyl-2-hydroxybenzylidene)amino)ethyl)-2-hydroxybenzamide, Ln = Dy(1), Gd(2), Er(3)) were successfully constructed via selective incorporation of groups with different coordination capabilities. These helicates with the well-defined conformation demonstrate high catalytic efficiency in converting CO2 to cyclic carbonates under mild conditions. Particularly, Zn3ErL4 showed superior catalytic performance with high catalytic activity (TOF up to 38?000 h-1) and extraordinary selectivity (up to 99%) across the wide substrate scope. Meanwhile, these 3d-4f helicates showed stable catalytic performance without being influenced by the moisture and air. The results presented herein highlight an important consideration for constructing heterometallic and asymmetric complexes for catalyzing CO2 conversion.
- Chen, Wanmin,Gao, Guoshu,Liu, Weisheng,Wang, Li,Yang, Huan
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- Phosphorus-based bifunctional organocatalysts for the addition of carbon dioxide and epoxides
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Bifunctional phosphonium salts were synthesized and employed as organocatalysts for the atom efficient synthesis of cyclic carbonates from CO2 and epoxides for the first time. These catalysts were obtained in high yields by a modular, straightforward one-step synthesis. The hydrogen-bond donating alcohol function in the side chain leads to a synergistic effect accelerating the catalytic reaction. The desired cyclic carbonates are obtained in high yields and selectivity under solvent-free reaction conditions without the use of any co-catalyst. Under optimized reaction conditions various epoxides were converted to the corresponding cyclic carbonates in excellent yields. The products were obtained analytically pure after simple filtration over a silica gel pad. This protocol is even applicable for a multigram reaction scale. Moreover, the catalysts could be easily recovered and reused up to five times.
- Werner, Thomas,Büttner, Hendrik
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- A multi-component polyoxometalate and its catalytic performance for CO2 cycloaddition reactions
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A multi-component polyoxometalate based on earth-abundant elements (NH4)10[Co8(H2O)10V10Mo23O104(OH)6]·34.5H2O (1) has been successfully obtained and characterized. Furthermore, compound 1 acted as a Lewis acid catalyst and promoted the conversion of carbon dioxide to a cyclic carbonate under mild reaction conditions.
- Chen, Shumin,Liu, Ying,Guo, Jipeng,Li, Pengzhen,Huo, Zhiyuan,Ma, Pengtao,Niu, Jingyang,Wang, Jingping
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- Hexanuclear 3d-4f complexes as efficient catalysts for converting CO2 into cyclic carbonates
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A series of novel hexanuclear 3d-4f complexes formulated as {[Ln2Zn4(μ3-OH)2L4(AcO)2(NO3)2(DMF)2]·2(CH3OH), LnIII = Dy3+ (1), Nd3+ (2), Tb3+ (3)} have been synthesized and characterized. These complexes 1-3 show excellent catalytic performance for the cycloaddition of CO2 and epoxides to obtain cyclic carbonates. The catalytic system has a wide substrate scope with high turnover numbers (9700) and high turnover frequencies (808 h-1) under mild conditions. Additionally, the catalysts could be conveniently prepared on a large scale and recycled.
- Gao, Guoshu,Wang, Li,Zhang, Ruilian,Xu, Cong,Yang, Huan,Liu, Weisheng
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- An Electrostatically Enhanced Phenol as a Simple and Efficient Bifunctional Organocatalyst for Carbon Dioxide Fixation
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An electrostatically enhanced phenol as a simple and competent bifunctional organocatalyst for the atom-economical conversion of epoxides to cyclic carbonates under environmentally benign conditions is described. Incorporating a positively charged center into phenols through a modular one-step synthesis results in a bifunctional system with enhanced acidity and reactivity, capable of epoxide activation, a halide nucleophilic ring-opening process, and CO2 incorporation in a synergistic fashion. A rational survey of the efficiency of different positively charged phenols and the influence of different parameters, such as temperature, catalyst loading, and the nature of the nucleophile, on catalytic activity was conducted. In addition, the time-dependent conversion of epoxide into the corresponding cyclic carbonate was further explored by FTIR-ATR and 1H NMR spectroscopy. This bifunctional catalytic platform is among one of the mildest and most efficient metal-free systems that is capable of converting a variety of epoxides into cyclic carbonates under virtually ambient conditions. The 1H NMR titration experiment validated the bifunctional catalytic mechanism wherein both the epoxide activation and the nucleophilic ring-opening process occur in concert en route to carbon dioxide fixation.
- Rostami, Ali,Mahmoodabadi, Mohammadali,Hossein Ebrahimi, Amir,Khosravi, Hormoz,Al-Harrasi, Ahmed
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- Imidazolium-based ionic liquid immobilized on functionalized magnetic hydrotalcite (Fe3O4/HT-IM): as an efficient heterogeneous magnetic nanocatalyst for chemical fixation of carbon dioxide under green conditions
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A reusable, eco-friendly, long-lived and efficient nanocatalyst, imidazolium-based ionic liquid immobilized on functionalized magnetic hydrotalcite (Fe3O4/HT-IM, IM is known as imidazolium-based melamine), was successfully introduced. The structure of the synthesized nanocatalyst was characterized by several techniques which revealed a plate-like shape with an average particle size of approximately 50 nm and also the presence of acidic sites (site density: 12 mmol g-1). The catalytic activity of Fe3O4/HT-IM was explored in the chemical fixation reaction of carbon dioxide towards the preparation of cyclic carbonates under optimized reaction conditions at 100 °C, 0.7 MPa and 1.6 mol% of the nanocatalyst. This reaction was conducted without using any metal, additive, toxic reagents and solvent/co-catalyst which provides mild and green conditions from the standpoint of green chemistry. Owing to having acidic-basic sites which can simultaneously accelerate the ring-opening of the epoxy ring and incorporation of CO2, this catalyst is attractive and suitable for this reaction. In particular, the prepared catalyst can be easily separated using an external magnetic field and reused over six times without any significant loss in catalytic performance and selectivity. This proves its great potential to be implemented for industrial purposes as a green catalyst. This journal is
- Khalifeh, Reza,Zarei, Zeinab,Rajabzadeh, Maryam
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- Enhancing the Catalytic Performance of Group I, II Metal Halides in the Cycloaddition of CO2to Epoxides under Atmospheric Conditions by Cooperation with Homogeneous and Heterogeneous Highly Nucleophilic Aminopyridines: Experimental and Theoretical Study
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Compared to metal-organic complexes and transition-metal halides, group I metal halides are attractive catalysts for the crucial cycloaddition reaction of CO2to epoxides as they are ubiquitously available and inexpensive, have a low molecular weight, and are not based on (potentially) endangered metals, especially for the case of sodium and potassium. Nevertheless, given their low intrinsic catalytic efficiency, they require the assistance of additional catalytic moieties. In this work, we show that by exploiting the high nucleophilicity of opportunely designed aminopyridines, catalytic systems based on alkaline metals can be formed, which allow the cycloaddition of CO2to epoxides to proceed under atmospheric pressure at moderate temperatures. Importantly, the aminopyridine nucleophiles can be applied in their heterogenized form, leading to a recyclable catalytic system. An investigation of the reaction mechanism by density functional theory calculations shows that metal halide complexes and nucleophilic pyridines can work as a dual cooperative catalytic system where the use of aminopyridines leads to lower energy barriers for the opening of the epoxide ring, and halide-adducts are involved in the subsequent steps of CO2insertion and ring closure.
- Natongchai, Wuttichai,Posada-Pérez, Sergio,Phungpanya, Chalida,Luque-Urrutia, Jesús Antonio,Solà, Miquel,D'Elia, Valerio,Poater, Albert
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p. 2873 - 2886
(2022/02/10)
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- Catalytic, Kinetic, and Mechanistic Insights into the Fixation of CO2 with Epoxides Catalyzed by Phenol-Functionalized Phosphonium Salts
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A series of hydroxy-functionalized phosphonium salts were studied as bifunctional catalysts for the conversion of CO2 with epoxides under mild and solvent-free conditions. The reaction in the presence of a phenol-based phosphonium iodide proceeded via a first order rection kinetic with respect to the substrate. Notably, in contrast to the aliphatic analogue, the phenol-based catalyst showed no product inhibition. The temperature dependence of the reaction rate was investigated, and the activation energy for the model reaction was determined from an Arrhenius-plot (Ea=39.6 kJ mol?1). The substrate scope was also evaluated. Under the optimized reaction conditions, 20 terminal epoxides were converted at room temperature to the corresponding cyclic carbonates, which were isolated in yields up to 99 %. The reaction is easily scalable and was performed on a scale up to 50 g substrate. Moreover, this method was applied in the synthesis of the antitussive agent dropropizine starting from epichlorohydrin and phenylpiperazine. Furthermore, DFT calculations were performed to rationalize the mechanism and the high efficiency of the phenol-based phosphonium iodide catalyst. The calculation confirmed the activation of the epoxide via hydrogen bonding for the iodide salt, which facilitates the ring-opening step. Notably, the effective Gibbs energy barrier regarding this step is 97 kJ mol?1 for the bromide and 72 kJ mol?1 for the iodide salt, which explains the difference in activity.
- Hu, Yuya,Wei, Zhihong,Frey, Anna,Kubis, Christoph,Ren, Chang-Yue,Spannenberg, Anke,Jiao, Haijun,Werner, Thomas
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p. 363 - 372
(2020/11/30)
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- Radii-dependent self-assembly polynuclear lanthanide complexes as catalysts for CO2transformation into cyclic carbonates
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Multidentate acylhydrazone ligand dinuclear and pentanuclear complexes were constructed with the lighter lanthanide ions (La3+, Pr3+, and Eu3+) and the heavier lanthanide ions (Tb3+ and Er3+), respectively, which indicated the structural change of polynuclear lanthanide complexes is controlled by the ionic radii of Ln3+ ions. In addition, these polynuclear lanthanide complexes as catalysts in combination with tetrabutylammonium bromide (TBAB) as a co-catalyst displayed excellent catalytic performance for CO2 conversion to obtain cyclic carbonates with a wide scope of substrates and high selectivity under solvent-free conditions. This journal is
- Chen, Changjuan,Zhang, Aijiang
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p. 20155 - 20163
(2021/12/02)
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- Method for preparing cyclic carbonate by immobilizing CO2 under catalysis of organic boric acid
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The invention discloses a synthesis method for synergistically catalyzing carbon dioxide immobilization through weak Lewis acid phenylboronic acid and tetrabutylammonium bromide. According to the method, CO2 is immobilized by epoxide, and a cyclic carbonate product is generated. The method comprises the following step: under the concerted catalysis of phenylboronic acid and tetrabutylammonium bromide, performing reaction on epoxide as shown in a formula IV, a formula V or a formula VI and carbon dioxide to respectively obtain a cyclic carbonate product as shown in a formula I, a formula II or a formula III. According to the method, raw materials are convenient and easy to obtain, reaction conditions are mild, operation is easy and convenient, and the yield can reach 97%.
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Paragraph 0179-0184
(2021/06/22)
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- The catalytic system ‘Rhodamine B/additive’ for the chemical fixation of CO2
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The catalytic system ‘Rhodamine B/additive’ was introduced to promote the CO2 reactions. We synthesized various cyclic carbonates in good to excellent yields under the catalysis of rhodamine B and TBAB. A variety of 2-oxazolidinone derivatives were obtained in the presence of rhodamine B and DBU.
- Wu, Feng-tian,Wu, Ling,Cui, Chun-na
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- Conversion of dilute CO2to cyclic carbonates at sub-atmospheric pressures by a simple indium catalyst
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The transformation of CO2to value added commodity chemicals presents an impactful strategy to obtain products that are less dependent on fossil fuels. In this study, indium tribromide (InBr3) mixed with tetrabutylammonium bromide (NBu4Br) co-catalyst has been identified as a simple, highly efficient catalyst for the synthesis of cyclic carbonates from epoxides and CO2at sub-atmospheric pressures, room temperature, and under solvent-free conditions. The InBr3/NBu4Br catalytic system is tolerant toward different functional groups with high conversions and >99% selectivity for cyclic carbonate without resorting to high pressures and temperatures. Moreover, a combination ofin situIR, NMR spectroscopy, and substrate labelling experiments enabled the proof of key catalytic steps and detection of reaction intermediates to elucidate the reaction mechanism. This technology represents a potential scalable system for the utilization of waste CO2
- Baalbaki, Hassan A.,Roshandel, Hootan,Hein, Jason E.,Mehrkhodavandi, Parisa
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p. 2119 - 2129
(2021/04/09)
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- Sustainable chemo-enzymatic synthesis of glycerol carbonate (meth)acrylate from glycidol and carbon dioxide enabled by ionic liquid technologies
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A sustainable chemo-enzymatic process for producing both glycerol carbonate acrylate (GCA) and glycerol carbonate methacrylate (GCMA), as useful monomers for the preparation of biodegradable plastic materials, has been carried out by taking advantage of ionic liquid (IL) technologies. The process consisted of two consecutive catalytic steps, which can be carried out by either sequential or one-pot experimental approaches. Glycidyl (meth)acrylate was firstly synthesized by enzymatic transesterification of (meth)acrylate vinyl ester with glycidol in Sponge Like Ionic Liquids (SLILs) as the reaction medium (100% yield after 6 h at 60 °C). SLILs not only provided a suitable reaction medium, but also allowed the simple isolation of the resulting glycidyl esters as an IL-free pure fraction through a straightforward cooling/centrifugation protocol. The second step consisted of the synthesis of GCA, or GCMA, as the outcome of the cycloaddition of CO2to the obtained glycidyl acrylate or glycidyl methacrylate, respectively, catalysed by a covalently attached 1-decyl-2-methylimidazolium moiety (Supported Ionic Liquid-Like Phase, SILLP) in a solvent-free system and under mild conditions (60 °C, 1-10 bar), leading to up to 100% yield after 6 h. The components of the reaction system (biocatalyst/SLIL/SILLP) can be fully recovered and reused for at least 6 cycles with unchanged catalytic performance.
- Donaire, Antonio,Garcia-Verdugo, Eduardo,Lozano, Pedro,Luis, Santiago V.,Nieto, Susana,Porcar, Raul,Villa, Rocio
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p. 4191 - 4200
(2021/06/17)
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- PROCESS FOR PREPARING GLYCEROL CARBONATE (METH)ACRYLATE
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The invention relates to a process for preparing glycerol carbonate (meth)acrylate by transesterification of methyl (meth)acrylate with glycerol carbonate in the presence of a zirconium acetylacetonate catalyst, wherein the catalyst is pretreated with 2% by weight to 25% by weight of water, based on the amount of catalyst.
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Page/Page column 6-11
(2021/04/30)
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- METHOD OF MAKING GLYCEROL CARBONATE (METH)ACRYLATE AND CURABLE COMPOSITIONS BASED THEREON
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Glycerol carbonate methacrylate may be prepared by reacting glycerol monomethacrylate and a carbonate such as a dialkyl carbonate in the presence of a catalyst and may be combined with an actinic radiation-curable oligomer, such as a (meth)acrylate-functionalized oligomer, and possibly other components to provide compositions capable of being cured, for example by exposure to actinic radiation, to obtain polymeric materials, such as 3D printed articles. The glycerol carbonate methacrylate reduces the viscosity of the composition, which may in the absence of the glycerol carbonate methacrylate be too high for the curable composition to be readily processed at room temperature, but additionally can impart a variety of other useful attributes to the curable compositions and cured products derived therefrom.
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Page/Page column 35
(2021/02/05)
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- An Aminopyridinium Ionic Liquid: A Simple and Effective Bifunctional Organocatalyst for Carbonate Synthesis from Carbon Dioxide and Epoxides
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An aminopyridinium ionic liquid is presented as a green, tunable, and active metal-free one-component catalytic system for the atom-efficient transformation of oxiranes and CO2 to cyclic carbonates. Inclusion of a positively charged moiety into aminopyridines, through a simple single-step synthesis, provides a one-component ionic liquid catalytic system with superior activity; effective in ring opening of epoxide, CO2 inclusion, and stabilization of oxoanionic intermediates. An efficiency assessment of a variety of positively charged aminopyridines was pursued, and the impact of temperature, catalyst loading, and the kind of nucleophile on the catalytic performance was also investigated. Under solvent-free conditions, this bifunctional organocatalytic system was used for the preparation of 18 examples of cyclic carbonates from a broad range of alkyl- and aryl-substituted oxiranes and CO2, where up to 98 percent yield and high selectivity were achieved. DFT calculations validated a mechanism in which nucleophilic ring-opening and CO2 inclusion occur simultaneously towards cyclic carbonate formation.
- Al-Harrasi, Ahmed,Ebrahimi, Amirhossein,Khosravi, Hormoz,Rezazadeh, Mostafa,Rostami, Ali
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p. 1587 - 1595
(2020/08/05)
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- Plasma-Assisted Immobilization of a Phosphonium Salt and Its Use as a Catalyst in the Valorization of CO2
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The first plasma-assisted immobilization of an organocatalyst, namely a bifunctional phosphonium salt in an amorphous hydrogenated carbon coating, is reported. This method makes the requirement for prefunctionalized supports redundant. The immobilized catalyst was characterized by solid-state 13C and 31P NMR spectroscopy, SEM, and energy-dispersive X-ray spectroscopy. The immobilized catalyst (1 mol %) was employed in the synthesis of cyclic carbonates from epoxides and CO2. Notably, the efficiency of the plasma-treated catalyst on SiO2 was higher than those of the SiO2 support impregnated with the catalyst and even the homogeneous counterpart. After optimization of the reaction conditions, 13 terminal and four internal epoxides were converted with CO2 to the respective cyclic carbonates in yields of up to 99 %. Furthermore, the possibility to recycle the immobilized catalyst was evaluated. Even though the catalyst could be reused, the yields gradually decreased from the third run. However, this is the first example of the recycling of a plasma-immobilized catalyst, which opens new possibilities in the recovery and reuse of catalysts.
- Brüser, Volker,Epping, Jan Dirk,Frank, Marcus,Hu, Yuya,Longwitz, Lars,Peglow, Sandra,Werner, Thomas
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- Cobalt-based catalytic system for the chemical fixation of CO2 under solvent-free conditions
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We have described a novel and efficient method for synthesizing cyclic carbonates with ‘Co (NO3)2 .6H2O/L6’-catalyzed coupling of epoxides and CO2 under solvent-free conditions. We proposed a possible reaction mechanism based on some control experiments. Phenylpropiolic acid could be provided by using the same method.
- Wu, Fengtian,Lin, Yu
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- PREPARATION OF (METH)ACRYLIC ACID ESTERS
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The invention relates to a method for preparation of (meth)acrylic acid esters from (meth)acrylic acid anhydrides.
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Page/Page column 12-14
(2020/03/05)
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- Cyclic amidine hydroiodide for the synthesis of cyclic carbonates and cyclic dithiocarbonates from carbon dioxide or carbon disulfide under mild conditions
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Hydroiodides of amidines can catalyze the reaction of carbon dioxide and epoxides under mild conditions such as ordinary pressure and ambient temperature, and the corresponding five-membered cyclic carbonates were obtained in high yields. The reaction of epoxide with carbon disulfide was also examined under the same conditions. Detailed investigation showed that the catalytic activity was highly affected by the counter anions of the amidine salts; the iodides were effective catalysts for both of the reaction of epoxide with carbon dioxide and carbon disulfide, whereas the bromide, chloride and fluoride counterparts exhibited almost no catalysis.
- Aoyagi, Naoto,Furusho, Yoshio,Endo, Takeshi
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supporting information
(2019/12/09)
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- Synthesis of well-defined yttrium-based Lewis acids by capturing a reaction intermediate and catalytic application for cycloaddition of CO2 to epoxides under atmospheric pressure
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Despite widespread use of yttrium halide complexes as powerful Lewis acids in catalysis, no strategies have yet been developed to prepare well-defined heterogeneous systems. Herein, we show that by applying the methodology of surface organometallic chemistry (SOMC), a readily available intermediate of the mechanism of the cycloaddition of CO2 to epoxides catalyzed by YCl3/TBAB (TBAB: tetrabutylammonium bromide) can be grafted on silica resulting in a well-defined complex [(SiO-)YCl(-OCH(CH3)CH2Cl)]. The complex was thoroughly characterized by means of elemental analysis, FT-IR, solid state (SS) NMR, XPS and XANES techniques. The thus-prepared surface complex serves as heterogeneous Lewis acid for the cycloaddition of CO2 to several epoxides under atmospheric pressure performing as a simple but efficient and recyclable material. Remarkably, the isolated complex prepared on highly dehydroxylated silica performed as the most efficient compound. Additional catalytic studies show that the yttrium complexes prepared in this study have the potential to be employed also as versatile Lewis acid catalyst for 5-hydroxymethyl furfural (HMF) reductive etherification. DFT calculations were carried out to investigate the possible grafting pathways and the mechanistic pathways of CO2-epoxide cycloaddition catalyzed by different surface model complexes.
- Sodpiban, Ounjit,Del Gobbo, Silvano,Barman, Samir,Aomchad, Vatcharaporn,Kidkhunthod, Pinit,Ould-Chikh, Samy,Poater, Albert,D'Elia, Valerio,Basset, Jean-Marie
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p. 6152 - 6165
(2019/11/14)
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- Life Cycle Assessment for the Organocatalytic Synthesis of Glycerol Carbonate Methacrylate
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Bifunctional ammonium and phosphonium salts have been identified as potential organocatalysts for the synthesis of glycerol carbonate methacrylate (GCMA). Three of these catalysts showed high efficiency and allowed the conversion of glycidyl methacrylate with CO2 to the desired product in >99 % conversion and selectivity. Subsequently, immobilized analogues of selected catalysts were prepared and tested. A phenol-substituted phosphonium salt on a silica support proved to be a promising candidate in recycling experiments. The same catalyst was used in 12 consecutive runs, resulting in GCMA yields of up to 88 %. Furthermore, a life cycle assessment was conducted for the synthesis of GCMA starting from epichlorohydrin (EPH) and methacrylic acid (MAA). For the functional unit of 1 kg GCMA, 15 wt % was attributed to the incorporation of CO2, which led to a reduction of the global warming potential of 3 % for the overall process.
- Büttner, Hendrik,Kohrt, Christina,Wulf, Christoph,Sch?ffner, Benjamin,Groenke, Karsten,Hu, Yuya,Kruse, Daniela,Werner, Thomas
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p. 2701 - 2707
(2019/06/13)
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- PROCESS FOR PREPARING CARBONATES BY ADDITION OF CO2 WITH AN EPOXIDE
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The invention relates to a process for preparing cyclic organic carbonates, characterized in that an epoxide is initially charged in the presence of CO2 and then a catalyst is added.
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Page/Page column 23-24
(2020/01/08)
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- Urethane compound and synthesis and application thereof
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The invention discloses a urethane compound and synthesis and application thereof. The urethane compound adopts the structure shown as a formula (1) or a formula (II); a synthesis method thereof comprises the following steps: synthesizing a cyclic carbonate intermediate from glycidyl methacrylate and CO2 as raw materials, and then performing a ring-opening reaction on the cyclic carbonate intermediate and a monoamino compound to obtain the urethane compound. Through improvement on a key molecular structure thereof, the overall process design of the synthesis method, and parameters and conditions of each step, the method is simple, the yield is high, the prepared urethane compound can be effectively applied to reinforcing and toughening modification of polypropylene carbonate, and the problems of unsatisfactory mechanical properties of the modified polypropylene carbonate and the like can be effectively solved.
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Paragraph 0054; 0055; 0059; 0063; 0067; 0071; 0075; 0079
(2018/08/04)
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- Poly(ethylene glycol)s as Ligands in Calcium-Catalyzed Cyclic Carbonate Synthesis
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Herein the use of CaI2 in combination with poly(ethylene glycol) dimethyl ether (PEG DME 500) as an efficient catalyst system for the addition of CO2 to epoxides is reported. This protocol is based on a nontoxic and abundant metal in conjunction with a polymeric ligand. Fifteen terminal epoxides were converted at room temperature to give the desired products in yields up to 99 %. Notably, this system was also effective for the synthesis of twelve challenging internal carbonates in yields up to 98 %.
- Steinbauer, Johannes,Werner, Thomas
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p. 3025 - 3029
(2017/08/18)
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- An in situ formed Ca2+-crown ether complex and its use in CO2-fixation reactions with terminal and internal epoxides
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Herein we report an efficient catalytic system based on readily available calcium iodide and 18-crown-6 ether for the atom economical addition of CO2 to epoxides. 1H NMR experiments revealed the selective in situ formation of a crown ether complex. This catalyst allows the conversion of various terminal epoxides under 1 atm CO2 pressure even at room temperature. Remarkably, a broad range of internal epoxides with various substitution patterns and substituents were smoothly converted which confirms the high efficiency and capability of the protocol. Notably, most of the internal carbonates were synthesized in high yields and diastereoselectivities of up to ≥99%. Furthermore, this system operates under solvent-free conditions without any co-catalysts e.g. onium salts.
- Steinbauer,Spannenberg,Werner
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supporting information
p. 3769 - 3779
(2017/08/26)
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- Transformation of carbon dioxide into valuable chemicals over bifunctional metallosalen catalysts bearing quaternary phosphonium salts
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The chemical transformation of CO2 under mild conditions remains a great challenge because of its exceptional kinetic and thermodynamic stability. Two important reactions in the transformation of CO2 are the N-formylation reaction of amines using hydrosilanes and CO2, and the cycloaddition of CO2 to epoxides. Here, we report the high efficiency of bifunctional metallosalen complexes bearing quaternary phosphonium salts in catalyzing both of these reactions under solvent-free, mild conditions without the need for co-catalysts. The catalysts' bifunctionality is attributed to an intramolecular cooperative process between the metal center and the halogen anion. Depending on the reaction, this activates CO2 by permitting either the synergistic activation of Si–H bond via metal–hydrogen coordinative bond (M–H) or the dual activation of epoxide via metal–oxygen coordinative bond (M–O). The one-component catalysts are also shown to be easily recovered and reused five times without significant loss of activity or selectivity. The current results are combined with previous work in the area to propose the relevant reaction mechanisms.
- Zhang, Wuying,Luo, Rongchang,Xu, Qihang,Chen, Yaju,Lin, Xiaowei,Zhou, Xiantai,Ji, Hongbing
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p. 736 - 744
(2017/04/24)
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- METHODS OF MAKING VINYL ESTER RESINS AND STARTING MATERIALS FOR THE SAME
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Various embodiments of the present invention relate to methods of making bis(hydroxyhydrocarbyl)ethers of bisphenols and vinyl ester resins. In various embodiments, the present invention provides a method for producing a vinyl ester resin (VER). The method can include a bisphenol or a bis(hydroxy((C1-C10)hydrocarbyl)ether of the bisphenol with a vinyl ester to form the VER.
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Paragraph 0086; 0088; 0092
(2017/07/14)
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- Convergent Activation Concept for CO2 Fixation in Carbonates
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Concepts to facilitate the conversion of epoxides with carbon dioxide to the corresponding cyclic carbonates commonly focus on the activation of the epoxide. Herein we report a catalytic system which allows the simultaneous activation of carbon dioxide and the epoxide. This convergent activation concept is realized by combining a suitable carbene as catalyst for the carbon dioxide activation with a second catalytic system based on potassium iodide for epoxide activation. Initial experiments showed synergistic effects and thus proving the feasibility of this activation concept. Moreover a standard protocol was developed and the substrate scope under these conditions has been studied. Under mild and solvent-free conditions 14 epoxides could be converted. The respective cyclic carbonates were obtained in good to excellent yields with selectivities ≥ 99 % after simple filtration.
- Desens, Willi,Werner, Thomas
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p. 622 - 630
(2016/02/27)
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- Synthesis of Cyclic Carbonates from Epoxides and Carbon Dioxide by Using Bifunctional One-Component Phosphorus-Based Organocatalysts
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Numerous bifunctional organocatalysts were synthesized and tested for the atom-efficient addition of carbon dioxide and epoxides to produce cyclic carbonates. These catalysts are based on phosphonium salts containing an alcohol moiety in the side chain for substrate activation through hydrogen bonding. In the model reaction, converting 1,2-butylene oxide with CO2, 19 catalysts were tested to determine structure-activity relationships. In total, 28 epoxides were converted with CO2 to give the respective cyclic carbonates in yields of up to 99%. Even at 45C, the most active catalyst was able to produce cyclic carbonates selectively in high yields. The carbonates were generally obtained as analytically pure products after simple filtration over silica gel. This single-component catalyst system works under neat and mild reaction conditions and tolerates several useful moieties. Two heads are better than one! Bifunctional organocatalysts are synthesized and tested in the catalytic reaction of epoxides and carbon dioxide to give the respective cyclic carbonates. Product formation is significantly increased by hydrogen-bond donation from the bifunctional phosphonium catalyst.
- Büttner, Hendrik,Steinbauer, Johannes,Werner, Thomas
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p. 2655 - 2669
(2015/09/02)
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