- Synthesis of Cyclic Carbonates from Carbon Dioxide and Epoxides in the Presence of Organoantimony Compounds as Novel Catalysts
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The reactions of carbon dioxide (1) with epoxides 2 to form cyclic carbonates 3 were carried out in the presence of organoantimony compounds as catalysts.Pentavalent organoantimony compounds, especially tetraphenylstibonium bromide (4b) and triphenylantimony dibromide (4d), are found to be more active catalysts than trivalent compounds, and the reactivity of compounds 2 seems to be in the following order: propylene oxide (2b) > styrene oxide (2d) > ethylene oxide (2a) > (chloromethyl)ethylene oxide (2c).The ring-opening polymerizations of 2b and 2d are also examined by using 4b and 4d, and it is found that they have no effect on the polymerization.On the basis of the results obtained, a reasonable scheme is proposed for the reaction.
- Nomura, Ryoki,Ninagawa, Akira,Matsuda, Haruo
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- Comprehensive insight into the support effect of graphitic carbon nitride for zinc halides on the catalytic transformation of CO2 into cyclic carbonates
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Chemical fixation of CO2 to high-valued chemicals is currently a significant research topic in both the environment and chemistry, and cycloaddition of CO2 with epoxides is regarded as a sustainable route for the manufacture of cyclic carbonates. Homogeneous catalysts including ionic liquids and organic metal complexes suffer from difficulty in catalyst-product separation despite their excellent catalytic activities. In this work, we utilized graphitic carbon nitride (g-C3N4) as a novel support to immobilize zinc halides (ZnX2) through a simple preparation method. Based on the detailed design of the synthesis of ZnX2/g-C3N4, the chemical bonding information of ZnX2 on g-C3N4 was comprehensively investigated by XPS and FT-IR techniques. In addition to activation of CO2, g-C3N4 can anchor zinc halides via interaction between zinc and nitrogen, thereby effectively alleviating potential leaching of zinc halides. As heterogeneous catalysts, ZnX2/g-C3N4 materials showed good catalytic activities in the cycloaddition reactions of CO2 with propylene oxide. Furthermore, a wide range of epoxides can be converted to the corresponding cyclic carbonate with good selectivities (>93%) and moderate conversions (50-88%).
- Xu, Jie,Gan, Yu-Lin,Hu, Peng,Zheng, Huan,Xue, Bing
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- Microporous Polymeric Spheres as Highly Efficient and Metal-Free Catalyst for the Cycloaddition of CO2 to Cyclic Organic Carbonates at Ambient Conditions
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Abstract: The cycloaddition of CO2 with epoxides to cyclic organic carbonates using metal-free heterogeneous catalysts is considered as a 100percent atom-economic and environmental-friendly route for CO2 utilization. Herein, we developed a metal-free microporous polymeric spheres catalyst (p-TBIB) by a simple Friedel–Crafts alkylation and applied in the cycloaddition of CO2 to cyclic organic carbonates. The catalyst shows high CO2 uptake (62.7?cm3?g?1, at 298?K and 1?bar), high selectivity over N2 (46 at 298?K) and perfect cycloaddition activities (66–97percent) and selectivities (over 99percent) and reusability (at least ten cycles) at ambient conditions (at 298?K and 1?bar). Graphic Abstract: [Figure not available: see fulltext.].
- Ding, Shunmin,Sun, Ling,Ma, Xiaohua,Cheng, Dan,Wu, Shaohua,Zeng, Rong,Deng, Shengjun,Chen, Chao,Zhang, Ning
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- Homogenous dual-ligand zinc complex catalysts for chemical fixation of CO2 to propylene carbonate
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Homogeneous dual-ligand zinc complex catalysts was developed for the synthesis of propylene carbonate (PC) through chemical fixation of CO2. It was found that among a number of various pKa N-donor ligands, the catalytic performance w
- Shi, Yan-Li,Zhang, Peng,Liu, Ding-Hua,Zhou, Peng-Fei,Sun, Lin-Bing
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- A simple synthesis of ethylene carbonate from carbon dioxide and 2-chloroethanol using silica gel as a catalyst
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A “green”, simple, technically and economically feasible synthesis of valuable ethylene carbonate from 2-chloroethanol and CO2 was developed using K2CO3 as a base, silica gel as a catalyst and under mild reaction conditions. The influence of reaction temperature, CO2 pressure, base and additives on conversion of 2-chloroethanol was studied.
- Lyubimov, Sergey E.,Zvinchuk, Anastasia A.,Sokolovskaya, Marina V.,Davankov, Vadim A.,Chowdhury, Biswajit,Zhemchugov, Pavel V.,Arzumanyan, Ashot V.
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- New mechanistic insight into the coupling reactions of CO2 and epoxides in the presence of zinc complexes
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Coupling reactions of CO2 and epoxide to produce cyclic carbonates were performed in the presence of a catalyst [L2ZnX2] (L = pyridine or substituted pyridine; X = Cl, Br, I), and the effects of pyridine and halide ligands on the catalytic activity were investigated. The catalysts with electron-donating substituents on pyridine ligands exhibit higher activity than those with unsubstituted pyridine ligands. On the other hand, the catalysts with electron-with-drawing substituents at the 2-position of the pyridine ligands show no activity; this demonstrates the importance of the basicity of the pyridine ligands. The catalytic activity of [L2ZnX2] was found to decrease with increasing electronegativity of the halide ligands. A series of highly active zinc complexes bridged by pyridinium alkoxy ions of the general formula [{(μ-OCHRCH2L)ZnBr2}] (n = 2 for R = CH3; n = 3 for R = H; L = pyridine or substituted pyridine) were synthesized and characterized by X-ray crystallography. The dinuclear zinc complexes obtained from propylene oxide adopt a square-planar geometry for the Zn2O2 core with two bridging pyridinium propoxy ion ligands. Trinuclear zinc complexes prepared from ethylene oxide adopt a boat geometry for the Zn3O2 core, in which three zinc and three oxygen atoms are arranged in an alternate fashion. These zinc complexes bridged by pyridinium alkoxy ions were also isolated from the coupling reactions of CO2 and epoxides performed in the presence of [L2ZnBr2]. Rapid CO2 insertion into the zinc-oxygen bond of the zinc complexes bridged by pyridinium alkoxy ions leads to the formation of zinc carbonate species; these which yield cyclic carbonates and zinc complexes bridged by pyridinium alkoxy ions upon interaction with epoxides. The mechanistic pathways for the formation of active species and cyclic carbonates are discussed on the basis of results from structural and spectroscopic analyses.
- Kim, Hoon Sik,Kim, Jai Jun,Lee, Sang Deuk,Lah, Myoung Soo,Moon, Dohyun,Jang, Ho Gyeom
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- Imidazolium ionic liquids/organic bases: Efficient intermolecular synergistic catalysts for the cycloaddition of CO2 and epoxides under atmospheric pressure
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An intermolecular synergistic catalytic system consisting of ionic liquids and organic bases is developed for the cycloaddition of CO2 and epoxides. This strategy realizes the cycloaddition takes place under atmospheric pressure of CO2 with high activity. NMR, FT-IR spectroscopy and DFT calculations are applied to investigate the synergistic effect and reaction mechanism on molecules. Plausible ionic liquids/secondary amines and ionic liquids/tertiary amines catalyzed mechanisms are proposed and further confirmed by more detailed DFT calculations including reaction pathways and energy profiles, respectively. The procedure reported here represents a facile, cost-effective and energy-efficient route for chemical fixation of CO2 into 5-membered cyclic carbonates.
- Ji, Liangzheng,Luo, Zhoujie,Zhang, Yongya,Wang, Rong,Ji, Yayan,Xia, Fei,Gao, Guohua
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- Realizing metal-free carbene-catalyzed carbonylation reactions with CO
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Many organic and main-group compounds, usually acids or bases, can accelerate chemical reactions when used in substoichiometric quantities, a process known as organocatalysis. In marked contrast, very few of these compounds are able to activate carbon monoxide, and until now, none of them could catalyze its chemical transformation, a classical task for transition metals. Herein we report that a stable singlet ambiphilic carbene activates CO and catalytically promotes the carbonylation of an oquinone into a cyclic carbonate. These findings pave the way for the discovery of metal-free catalyzed carbonylation reactions.
- Peltier, Jesse L.,Eder Tomás-Mendivil,Tolentino, Daniel R.,Hansmann, Max M.,Jazzar, Rodolphe,Bertrand, Guy
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- Stereochemistry of copper- and nickel-catalyzed insertion of carbon dioxide into epoxides. A microwave study
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Reaction of trans-1,2-dideuterioethene oxide (1) with carbon dioxide, using copper and nickel catalysts, and subsequent analysis of the product ethene carbonate-d2 (2) by microwave spectroscopy, shows that the copper-catalyzed reaction is stereo-specific (retention) whereas the nickel-catalyzed reaction is non-stereospecific.
- Baeckvall, Jan-E.,Karlsson, Ola,Ljunggren, Stig O.
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- Formation of Cyclic Carbonates from CO2 and Epoxides Catalyzed by a Cobalt-Coordinated Conjugated Microporous Polymer
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An inexpensive and effective cobalt coordinated conjugated microporous polymer (Co-CMP-2) made up from cross-linked an ethanediamine-based salen ligand with 1,3,5-triethynylbenzene. Co-CMP-2 exhibited extremely high catalytic efficiency in the synthesis of cyclic carbonates from CO2 and epoxides, which is superior to that of previously reported Co-CMP. Co-CMP-2 achieved a TOF of 23300 h?1 for ethylene carbonate. Moreover, the catalyst can be reused more than 10 times without significant loss in activity.
- Xiong, Jian,Yang, Rui-Xia,Xie, Yong,Huang, Nian-Yu,Zou, Kun,Deng, Wei-Qiao
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- Water as an efficient medium for the synthesis of cyclic carbonate
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Herein, we report a novel method for the synthesis of cyclic carbonate in water. By tuning the amount of water, cycloaddition of CO2 to epoxide in aqueous medium leads to cyclic carbonates with moderate to excellent yields and high selectivities. In addition, the presence of water could remarkably improve the activity of ionic liquids by which the turnover frequency of the reaction is about 4-5 times higher in the presence than in the absence of water. The relationship between the higher catalytic reactivity and water was proposed.
- Sun, Jian,Ren, Junyi,Zhang, Suojiang,Cheng, Weiguo
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- UV-vis spectroscopy of iodine adsorbed on alkali-metal-modified zeolite catalysts for addition of carbon dioxide to ethylene oxide
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The basicity of alkali-metal-exchanged (Na, K, Cs) zeolites X and Y was probed by UV-vis diffuse reflectance spectroscopy of adsorbed iodine. The observed blue shift in the visible absorption spectrum of adsorbed iodine, compared to gaseous iodine, correlated well with the negative charge on the framework oxygen atoms calculated from the Sanderson electronegativity equalization principle. The blue shifts associated with iodine adsorbed on classical catalytic supports like silica, alumina, and magnesia suggest that the iodine adsorption technique for probing basicity is applicable to a wide variety of solids. Iodine was also adsorbed on X and Y zeolites containing occluded cesium oxide formed by decomposition of impregnated cesium acetate. However, the iodine appeared to irreversibly react on these strongly basic samples, possibly forming an adsorbed triiodide ion. As a complement to the adsorption studies, the activity of alkali-metal-containing zeolites for the base-catalyzed formation of ethylene carbonate from ethylene oxide and carbon dioxide was investigated. Among the ion-exchanged zeolites, the cesium form of zeolite X exhibited the highest activity for ethylene carbonate formation. The catalytic activity of a zeolite containing occluded cesium was even higher than that of a cesium-exchanged zeolite. The presence of water adsorbed in zeolite pores promoted the rate of ethylene carbonate formation for both cesium-exchanged and cesium-impregnated zeolite X.
- Doskocil, Eric J.,Bordawekar, Shailendra V.,Kaye, Brian G.,Davis, Robert J.
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- Guanidinium salt functionalized PEG: An effective and recyclable homogeneous catalyst for the synthesis of cyclic carbonates from CO2 and epoxides under solvent-free conditions
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A guanidinium bromide covalently bound to CO2-philic polyethylene glycol (PEG) is proved to be a highly effective homogeneous catalyst for the eco-friendly synthesis of cyclic carbonates from carbon dioxide and epoxides under mild conditions, which requires no additional organic solvents or co-catalyst. Notably, it has been found that there is a pronouncedly cooperative effect between the catalyst part and the support part. Moreover, the catalyst is able to be reused with retention of high catalytic activity and selectivity. This process looks promising as a strategy for homogeneous catalyst recycling. Georg Thieme Verlag Stuttgart.
- Dou, Xiao-Yong,Wang, Jin-Quan,Du, Ya,Wang, Er,He, Liang-Nian
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- Immobilization poly(ionic liquid)s into hierarchical porous covalent organic frameworks as heterogeneous catalyst for cycloaddition of CO2 with epoxides
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The chemical fixation of CO2 into high value-added chemicals is of significant potential and sustainability to address the energy and ecological issues. To achieve great catalytic performance on the transformation of CO2, it is pivotal to strategically integrating several multifunctional and synergetic functionalities into the catalyst design and catalytic system construction. Herein, the poly(ionic liquid)-hierarchical porous covalent organic framework (PIL-HPCOF) hybrids were successfully synthesized via the formation of HPCOF through hard-template method, followed by in-situ polymerization of mono-vinyl decorated ionic liquids (ILs). The resultant PIL-HPCOF hybrids possess excellent versatility, with micropores providing high surface area to enhance CO2 uptake capacity and macropores supplying sufficient pore volume to promote mass transport of substrates. As a proof of concept, the conversion of CO2 with epoxides to produce cyclic carbonates was selected as a model reaction, which catalytic performance was obviously promoted by using PIL-HPCOF hybrids as the catalyst as compared to those of independent PIL and the PIL-COF hybrids with only micropores. Thus, it enables such a metal-free catalysis proceeds under much mild conditions (CO2 (1 MPa), 90 °C) and with broad substrates tolerance. These results supply the basis to design efficient and stable catalysts for CO2 conversion.
- Du, Yi-Ran,Guan, Peng-Xin,Wang, Rui,Wang, Yao-Feng,Xu, Bao-Hua,Yang, Xin
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- Method for preparing cyclic carbonate through catalysis of hydrogen bond donor functionalized polymeric ionic liquid
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The invention provides a preparation method of a hydrogen bond donor functionalized polymerization ionic liquid catalyst, and a method for synthesizing cyclic carbonate by catalyzing CO2 and epoxide with the catalyst. According to the method, an imidazolyl ionic liquid monomer and a hydrogen bond donor monomer are subjected to cross-linking polymerization in proportion to form the polymerized ionic liquid catalyst, the catalyst can efficiently catalyze CO2 and epoxide to be converted into cyclic carbonate under the optimal reaction condition, and the yield can reach 99%. Compared with a traditional catalyst, the polymerization ionic liquid catalyst has the advantages that a hydrogen bond donor and ionic liquid are effectively combined in a free radical polymerization manner to form a heterogeneous catalyst which has the advantages of rich hydrogen bond donor, dispersed active sites, good catalytic effect, simple preparation method, good cycle performance, simple separation and the like, and huge industrial application potential is achieved.
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Paragraph 0049-0092
(2021/02/10)
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- METHOD FOR PRODUCING CARBONATE DERIVATIVE
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The objective of the present invention is to provide a method for producing a polycarbonate safely and efficiently even without using a base. The method for producing a carbonate derivative according to the present invention is characterized in comprising the step of irradiating a high energy light to a composition comprising the halogenated methane and the hydroxy group-containing compound in the presence of oxygen, wherein a molar ratio of a total usage amount of the hydroxy group-containing compound to 1 mole of the halogenated methane is 0.05 or more.
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- Method for preparing cyclic carbonate from quaternary phosphonium salt
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The invention provides a method for preparing a cyclic carbonate by using a quaternary phosphonium salt in order to overcome the problems of insufficient catalyst activity and low yield of a target product in the existing process for preparing a cyclic carbonate by using a quaternary phosphonium salt catalyst, and adopts the quaternary phosphonium salt shown 1 as a catalyst by using carbon dioxide and an epoxy compound as reactants. Without solvent, carbon dioxide is reacted with the epoxy compound to form a cyclic carbonate. The method for preparing the cyclic carbonate by the quaternary phosphonium salt adopts the quaternary phosphonium salt represented by the structural formula 1 as a catalyst, has obviously excellent catalytic activity, and improves the selectivity of the target product.
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Paragraph 0046; 0065; 0069-0076; 0084-0085; 0098-0099
(2021/08/25)
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- Method for catalytically synthesizing cyclic carbonate based on multi-active-center type ionic liquid
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The invention discloses a method for catalytically synthesizing cyclic carbonate based on multi-active-center type ionic liquid. A series of multi-active-center type ionic liquids are designed, efficient conversion of cyclic carbonate can be achieved in a short time under the condition that the use amount of the ionic liquids is very small in the reaction, and the stability and the activity of theionic liquids are superior to those of single-active-center type ionic liquids. The method is characterized by comprising two stages: an ionic liquid synthesis stage and a catalytic cycloaddition reaction stage. In the synthesis stage of the ionic liquid, the reaction is carried out in a nitrogen atmosphere, the reaction temperature is 20-200 DEG C, the reaction pressure is normal pressure, and the reaction time is 1-48 hours, so that the multi-active-center type ionic liquid is obtained; wherein the catalytic cycloaddition reaction stage comprises that the ionic liquid is adopted as a catalyst, the reaction temperature is 30-180 DEG C, the reaction pressure is 0.1-8 MPa, the reaction time is 0.25-24 h, the product cyclic carbonate is obtained, and the anion of the ionic liquid can promote the ring opening of the epoxy compound in the process. The catalytic process has the following advantages that through the design of a multi-active center site structure, efficient conversion of thereaction is achieved, meanwhile, cyclic carbonate can also be used as a raw material source of efficient chemicals such as downstream dimethyl carbonate and ethylene glycol, and good economical efficiency and energy saving performance are achieved.
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Paragraph 0065; 0103-0105
(2021/01/29)
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- Capturing ethylene glycol with dimethyl carbonate towards depolymerisation of polyethylene terephthalate at ambient temperature
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Depolymerisation of polyethylene terephthalate (PET) via alkali metal alkoxide catalysed methanolysis efficiently proceeded at ambient temperature by capturing ethylene glycol (EG) with dimethyl carbonate (DMC), which biased the equilibrium toward dimethy
- Nakajima, Yumiko,Sato, Junichi,Tanaka, Shinji
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supporting information
p. 9412 - 9416
(2021/12/09)
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- Method for synthesizing cyclic carbonate by using metalloporphyrin ion framework to catalyze urea and dihydric alcohol
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The invention relates to a method for preparing cyclic carbonate by using a metalloporphyrin ion framework catalyst. The method is characterized in that urea and a dihydric alcohol compound are subjected to urea alcoholysis reaction under the catalysis of the catalyst to obtain the cyclic carbonate, wherein the catalyst is a metalloporphyrin ion framework heterogeneous catalyst, and the cyclic carbonate prepared by the method has high yield. The method has the characteristics that compared with a traditional catalyst, the used metalloporphyrin ion framework heterogeneous catalyst has multiple active sites, double active components, high catalytic efficiency and stable performance, is easy to separate and recycle from a reaction solution, and has a relatively high industrial application value.
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Paragraph 0041-0072
(2021/08/28)
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- CO2atmosphere enables efficient catalytic hydration of ethylene oxide by ionic liquids/organic bases at low water/epoxide ratios
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The development of an efficient and low-cost strategy for the production of monoethylene glycol (MEG) through hydration of ethylene oxide (EO) at low H2O/EO molar ratios is an important industrial challenge. We have established that by using CO2as the reaction atmosphere, hydration of EO can be achieved at a low H2O/EO ratio of 1.5?:?1 along with high yields (88-94%) and selectivities (91-97%) of MEG catalyzed by binary catalysts of ionic liquids and organic bases. The results are significantly better than those of experiments conducted under an atmosphere of N2. Isotope labeling experiments revealed that CO2had altered the reaction pathway and participated in the reaction, in which cycloaddition of EO with CO2occurred first followed by the hydrolysis of ethylene carbonate (EC) to generate MEG and recover CO2. The ionic liquids and organic bases synergistically catalyzed the one-pot two-step reaction. DFT calculations confirmed that this route is more kinetically favorable compared to the pathway of direct epoxide hydration.
- Ding, Tong,Gao, Guohua,Xia, Fei,Yuan, Huixia,Zha, Jinyin,Zhang, Dawei,Zhang, Jingshun
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supporting information
p. 3386 - 3391
(2021/05/25)
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- Room temperature and normal pressure preparation method of organic carbonate
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The invention relates to the technical field of organic synthesis, and provides a room temperature and normal pressure preparation method of organic carbonate. The method comprises the following steps: introducing carbon dioxide into an imidazole ionic liquid to obtain a mixture; mixing the obtained mixture with alcohol and halogenated hydrocarbon, and carrying out addition-substitution reactionsto obtain organic carbonate. The whole reaction process is carried out at a room temperature under a normal pressure. The activation energy of the reaction is reduced by using imidazole ionic liquid and halogenated hydrocarbon, and finally, organic carbonate is prepared from CO2 at a room temperature under a normal pressure.
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Paragraph 0112-0114
(2020/07/15)
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- Biomass-derived Cu/porous carbon for the electrocatalytic synthesis of cyclic carbonates from CO2and diols under mild conditions
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Biomass-derived Cu/porous carbon (Cu/PC) composites were facilely assembled by using a one-pot hydrothermal approach combined with calcination under a N2 atmosphere, and were used for the electrocatalytic synthesis of cyclic carbonates from CO2 and diols at room temperature and normal pressure without any other catalysts. The results show that the Cu/PC composites with large specific surface areas (SBET > 279 m2 g-1) and high pore volumes (Vp > 0.47 cm3 g-1) possess good catalytic activity for CO2 electrocatalytic fixation. The Cu nanoparticles were uniformly dispersed in the PC, resulting in a remarkable increase in the catalytic activity of the composite compared with those of pure PC and Cu sheets. In addition, the Cu content influenced the electrocatalytic activity. Among the materials used, Cu/PC-III was the best cathode as it had a 46.3percent electrosynthesis yield of propylene carbonate, wide application prospects and was suitable for the synthesis of other o-diols. The yield of 4-propyl-1,3-dioxolan-2-one reached 57.8percent. The prepared composites also displayed satisfactory reusability, and the yield was not reduced even after six cycles of use. These results reveal that the composites could be effectively used for the electrosynthesis of cyclic carbonates from CO2 and diols under mild conditions.
- Zhang, Jing-Jie,Li, Shi-Ming,Shi, Yi,Hu, Qiao-Li,Wang, Huan,Lu, Jia-Xing
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p. 11817 - 11823
(2020/07/27)
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- CARBONATE DERIVATIVE PRODUCTION METHOD
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The objective of the present invention is to provide a method for producing a carbonate derivative in a safe and efficient manner. The method for producing a carbonate derivative according to the present invention is characterized in comprising irradiating light on a composition containing a C1-4 halogenated hydrocarbon having one or more kinds of halogen atoms selected from the group consisting of a chlorine atom, a bromine atom and an iodine atom, a nucleophilic functional group-containing compound and the specific base in the presence of oxygen.
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Paragraph 0114-0117
(2020/04/09)
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- Spatially Ordered Arrangement of Multifunctional Sites at Molecule Level in a Single Catalyst for Tandem Synthesis of Cyclic Carbonates
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With fossil energy resources increasingly drying up and gradually causing serious environmental impacts, pursuing a tandem and green synthetic route for a complex and high-value-Added compound by using low-cost raw materials has attracted considerable attention. In this regard, the selective and efficient conversion of light olefins with CO2 into high-value-Added organic cyclic carbonates (OCCs) is of great significance owing to their high atom economy and absence of the isolation of intermediates. To fulfill this expectation, a multifunctional catalytic system with controllable spatial arrangement of varied catalytic sites and stable texture, in particular, within a single catalyst, is generally needed. Here, by using a stepwise electrostatic interaction strategy, imidazolium-based ILs and Au nanoparticles (NPs) were stepwise immobilized into a sulfonic group grafted MOF to construct a multifunctional single catalyst with a highly ordered arrangement of catalytic sites. The Au NPs and imidazolium cation are separately responsible for the selective epoxidation and cycloaddition reaction. The mesoporous cage within the MOF enriches the substrate molecules and provides a confined catalytic room for the tandem catalysis. More importantly, the highly ordered arrangement of the varied active sites and strong electrostatic attraction interaction result in the intimate contact and effective mass transfer between the catalytic sites, which allow for the highly efficient (>74% yield) and stable (repeatedly usage for at least 8 times) catalytic transformation. The stepwise electrostatic interaction strategy herein provides an absolutely new approach in fabricating the controllable multifunctional catalysts, especially for tandem catalysis.
- Chang, Gang-Gang,Chen, Jian,Huang, Ke-Xin,Ke, Shan-Chao,Li, Jia-Xin,Luo, Ting-Ting,Ma, Xiao-Chen,Wu, Jian,Yang, Xiao-Yu
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- Modified polyether glycols supported ionic liquids for CO2 adsorption and chemical fixation
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Hydroxyl polyether-grafted imidazolium ionic liquids (HPEGnRIMX) have been synthesized by a chemical stoichiometric method, which were applied into strengthening CO2 accessibility and conversing CO2 into cyclic carbonates.
- Liu, Ying,Song, Yan,Zhou, Jianhua,Zhang, Xiangping
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- A non-metal Acen-H catalyst for the chemical fixation of CO2 into cyclic carbonates under solvent- and halide-free mild reaction conditions
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A metal-free Acen-H catalyst was effectively synthesized by a single step reflux method and successfully tested for the cycloaddition of CO2 with epoxides to synthesize cyclic carbonates. The Acen-H catalyst exhibited high activity and selectivity for the cycloaddition reaction in the absence of co-catalysts (halides) and solvents at mild reaction conditions of a reaction temperature of 110 °C and a reaction pressure of 1 MPa. Under the optimized reaction conditions, some of the epoxides were successfully converted into corresponding cyclic carbonates with a highest yield of ～98.5%. The composition and structure of the homogeneous catalyst was then systematically evaluated and the reaction kinetics and a plausible reaction mechanism for the cycloaddition of CO2 with epoxides were proposed. The density functional theory (DFT) calculation provided a corroborated elucidation for the proposed mechanism. The catalytic activity of the Acen-H catalyst was found to be originated from the active hydrogen bond donors (-O-H, =N---H) and imino groups present (-N=) in it, which played a synergistic role in the adsorption and activation of reactants as confirmed by the DFT studies. The structural characteristics of the catalyst was found to be crucial for the cycloaddition of CO2 with epoxides.
- Chen, Shiyu,Jia, Qingming,Liu, Yi,Pudukudy, Manoj,Shan, Shaoyun,Wang, Junya,Yue, Zhongxiao,Zhao, Wenbo
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- Scalable, Durable, and Recyclable Metal-Free Catalysts for Highly Efficient Conversion of CO2 to Cyclic Carbonates
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A series of highly active organoboron catalysts for the coupling of CO2 and epoxides with the advantages of scalable preparation, thermostability, and recyclability is reported. The metal-free catalysts show high reactivity towards a wide scope of cyclic carbonates (14 examples) and can withstand a high temperature up to 150 °C. Compared with the current metal-free catalytic systems that use mol % catalyst loading, the catalytic capacity of the catalyst described herein can be enhanced by three orders of magnitude (epoxide/cat.=200 000/1, mole ratio) in the presence of a cocatalyst. This feature greatly narrows the gap between metal-free catalysts and state-of-the-art metallic systems. An intramolecular cooperative mechanism is proposed and certified on the basis of investigations on crystal structures, structure–performance relationships, kinetic studies, and key reaction intermediates.
- Li, Bo,Wu, Guang-Peng,Xie, Rui,Yang, Guan-Wen,Yang, Li,Zhang, Yao-Yao
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supporting information
p. 23291 - 23298
(2020/10/19)
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- Highly synergistic effect of ionic liquids and Zn-based catalysts for synthesis of cyclic carbonates from urea and diols
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The development of stable and efficient catalysts is an attractive topic for green chemistry reactions under mild reaction conditions. In order to improve solvent-free synthesis of cyclic carbonates from urea and diols, a binary catalyst systems of Zn-based and different ionic liquids (ILs) were developed and examined in this study. The yield of ethylene carbonate (EC) could reach to 92.2% in the presence of C16mimCl/ZnCl2 catalyst. Through exploring the structure-activity relationships of cation and anion, it was confirmed that a synergistic effect of cation and anion of catalyst had important influences on urea alcoholysis. Additionally, the controlling step of EC synthesis reaction involving the elimination of an ammonia molecule from intermediates had been revealed by in situ FT-IR. This could afford a guided insight for synthesizing cyclic carbonates with high yield. Furthermore, a possible mechanism for the catalytic process was proposed based on DFT and the experimental results via FT-IR, 1H-NMR and 13C NMR analysis, which revealed that not only a probable synergistic effects of cation-anion matters, but also C(2)-H of ILs and Zn2+ played a key role in accelerating the reaction of urea alcoholysis. This catalytic mechanism study is to provide a preliminary basis to develop novel catalysts for cyclic carbonates from urea and diols through a green synthetic pathway.
- Cheng, Weiguo,Deng, Lili,Dong, Li,He, Hongyan,Li, Zengxi,Qian, Wei,Shi, Zijie,Su, Qian,Sun, Wenzhong
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- METHOD FOR PRODUCING AROMATIC NITRILE COMPOUND AND METHOD FOR PRODUCING CARBONATE ESTER
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Provided is a method for regenerating an aromatic amide compound into a corresponding aromatic nitrile compound, the method realizing a dehydration reaction of providing a target compound selectively at a high yield with generation of a by-product being suppressed. Also provided is a method for producing an aromatic nitrile compound that decreases the number of steps of dehydration reaction and significantly improves the reaction speed at a pressure close to normal pressure. Furthermore, the above-described production method is applied to a carbonate ester production method to provide a method for producing carbonate ester efficiently. The above-described objects are achieved by a method for producing an aromatic nitrile compound including a dehydration reaction of dehydrating an aromatic amide compound, in which the dehydration reaction uses diphenylether.
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Paragraph 0113
(2019/07/03)
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- METHOD FOR PRODUCING AROMATIC NITRILE COMPOUND AND METHOD FOR PRODUCING CARBONIC ACID ESTER
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Provided is a method for regenerating an aromatic amide compound into a corresponding aromatic nitrile compound, the method realizing a dehydration reaction of providing a target compound selectively at a high yield, with generation of a by-product being suppressed. Also provided is a method for producing an aromatic nitrile compound that decreases the number of steps of the dehydration reaction and significantly improves the reaction speed even at a pressure close to normal pressure. In addition, the above-described production method is applied to a carbonate ester production method to provide a method for producing a carbonate ester efficiently. The above-described methods are realized by a method for producing an aromatic nitrile compound including a dehydration reaction of dehydrating an aromatic amide compound, in which the dehydration reaction uses, as a solvent, any of 1,2-dimethoxybenzene, 1,3-dimethoxybenzene and 1,3,5-trimethoxybenzene.
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Paragraph 0165-0166
(2020/01/08)
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- Visible-Light-Mediated Liberation and In Situ Conversion of Fluorophosgene
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The first example for the photocatalytic generation of a highly electrophilic intermediate that is not based on radical reactivity is reported. The single-electron reduction of bench-stable and commercially available 4-(trifluoromethoxy)benzonitrile by an organic photosensitizer leads to its fragmentation into fluorophosgene and benzonitrile. The in situ generated fluorophosgene was used for the preparation of carbonates, carbamates, and urea derivatives in moderate to excellent yields via an intramolecular cyclization reaction. Transient spectroscopic investigations suggest the formation of a catalyst charge-transfer complex-dimer as the catalytic active species. Fluorophosgene as a highly reactive intermediate, was indirectly detected via its next downstream carbonyl fluoride intermediate by NMR. Furthermore, detailed NMR analyses provided a comprehensive reaction mechanism including a water dependent off-cycle equilibrium.
- Petzold, Daniel,Nitschke, Philipp,Brandl, Fabian,Scheidler, Veronica,Dick, Bernhard,Gschwind, Ruth M.,K?nig, Burkhard
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supporting information
p. 361 - 366
(2018/11/23)
-
- Versatile and scalable synthesis of cyclic organic carbonates under organocatalytic continuous flow conditions
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The benchmark route for the preparation of cyclic organic carbonates starts from toxic, volatile and unstable epoxides. In this work, cyclic organic carbonates are prepared according to alternative sustainable and intensified continuous flow conditions from the corresponding 1,2-diols. The process utilizes dimethyl carbonate (DMC) as a low toxicity carbonation reagent and relies on the organocatalytic activity of widely available and cheap organic ammonium and phosphonium salts. Glycerol is selected as a model substrate for preliminary optimization with a library of homogeneous ammonium and phosphonium salts. The nature of the anion dramatically influences the catalytic activity, while the nature of the cation does not impact the reaction. Upon optimization, glycerol carbonate is obtained in 95% conversion and 79% selectivity within 3 min residence time at 180 °C (11 bar) with 3.5 mol% of tetrabutylammonium bromide as the organocatalyst. A straightforward liquid-liquid extraction procedure enables both the purification of glycerol carbonate and the recycling of the homogeneous catalyst. The conditions are amenable to refined and crude bio-based glycerol, although conversions are lower in the latter case. Control experiments suggest that water present in the crude samples induces significant hydrolysis of glycerol carbonate. The reaction conditions are then successfully applied on a wide variety of substrates, affording the corresponding cyclic carbonates in overall good to excellent yields (20 examples, 45-95%). The substrate scope notably encompasses bio-based starting materials such as glycerol ethers and erythritol-derived diols. In-line NMR is featured as a qualitative analytical tool for real-time reaction monitoring. The scalability of this carbonation procedure on glycerol is assessed in a commercial pilot-scale silicon carbide continuous flow reactor of 60 mL internal volume. Glycerol carbonate is obtained in 76% yield, corresponding to a productivity of 13.6 kg per day.
- Gérardy, Romaric,Estager, Julien,Luis, Patricia,Debecker, Damien P.,Monbaliu, Jean-Christophe M.
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p. 6841 - 6851
(2019/12/24)
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- Novel and effective strategy of dual bis(trifluoromethylsulfonyl)imide imidazolium ionic liquid immobilized on periodic mesoporous organosilica for greener cycloaddition of carbon dioxide to epoxides
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Novel periodic mesoporous organosilica supported nanocatalysts with different loading levels of a bis(trifluoromethylsulfonyl)imide anion-based dual imidazolium ionic liquid have been prepared and evaluated as efficient catalysts for the cycloaddition of CO2 to epoxides. The as-fabricated PMO@IL-NTf2(1.0) exhibited the best catalytic performance with excellent conversions (98-100%) and yields (96-99%) at 90 °C and 0.6 MPa for 0.5-1 h, based on a synergistic effect between the dual nucleophilic anion sites of the imidazolium ionic liquid and the hydroxyl group sites of periodic mesoporous organosilica. The excellent recyclability and operational simplicity make this protocol economic and environment-friendly.
- Jin, Tan,Dong, Fang,Liu, Yang,Hu, Yu Lin
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p. 2583 - 2590
(2019/02/12)
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- Synergistic cooperation of bi-active hydrogen atoms in protic carboxyl imidazolium ionic liquids to push cycloaddition of CO2 under benign conditions
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Nine protic carboxyl imidazolium ionic liquids are synthesized. Then, they are employed to catalyze the chemical fixation of carbon dioxide (CO2) and propylene oxide leading to propylene carbonate in the absence of co-catalyst and organic solvent. HCPImBr presents the best catalytic activity with the product yield of 92% under reaction temperature 120 °C, CO2 initial pressure 1.5 MPa, catalyst amount 0.5 mol%, and reaction time 2.0 h. Even if the reaction temperature and CO2 initial pressure are decreased to 80 °C and 1.0 MPa, respectively, the 85% of product yield would be kept with the 1.0% catalyst dosage along with 12.0 h. With the exception of the most optimal reaction conditions, generality, and recyclability of HCPImBr are also investigated. More importantly, the reaction mechanism is investigated by the density functional theory, which is the first time to report the mechanism for protic carboxyl imidazolium ionic liquids. The catalytic activity of ionic liquids would be further improved with the reasonable combination of cation and anion.
- Wang, Tengfei,Zhu, Xinrui,Mao, Lemin,Liu, Yi,Ren, Tiegang,Wang, Li,Zhang, Jinglai
-
-
- Hydroxyl-functionalized pyrazolium ionic liquids to catalyze chemical fixation of CO2: Further benign reaction condition for the single-component catalyst
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Lots of ionic liquids have been utilized as catalyst for the coupling reaction of carbon dioxide with epoxides, however, catalyzed conditions could not be regarded as benign, especially when no co-catalyst and/or organic solvent is involved. A series of hydroxyl-functionalized pyrazolium ionic liquids are firstly synthesized. They would efficiently catalyze the cycloaddition of carbon dioxide and propylene oxide under 110 °C and 1.0 MPa carbon dioxide initial pressure with 1 mol% catalyst during 4 h resulting in the product yield of 91.2%. The catalytic condition is greatly refined as compared with other single-component ionic liquids with simple anion. Simultaneously, the effect of reaction temperature, amount of catalyst, carbon dioxide initial pressure, and reaction time is explored along with the reusability of catalyst. For most of epoxides with terminal substituted group, HEEPzBr presents acceptable catalytic activity. The difference of HEMPzBr, HEEPzBr, and HPEPzBr is also explored by the density functional theory calculations.
- Wang, Tengfei,Ma, Yuan,Jiang, Jiamin,Zhu, Xinrui,Fan, Baowan,Yu, Guanyao,Li, Ningning,Wang, Shasha,Ren, Tiegang,Wang, Li,Zhang, Jinglai
-
-
- Highly regio- And stereoselective synthesis of cyclic carbonates from biomass-derived polyols: Via organocatalytic cascade reaction
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The cascade reaction of CO2, vicinal diols, and propargylic alcohol, was firstly achieved by dual Lewis base (LB) organocatalytic systems involving LB-CO2 adducts and commercially available organic amines. This methodology could overcome the chemical inertness of CO2, providing an alternative route to various functionalized five-membered cyclic carbonates in moderate to high yields under mild reaction conditions (25 °C, 1.0 atm of CO2). More importantly, this method could also be applied for facile and efficient synthesis of chiral polycyclic carbonates from biomass-derived polyols with complete configuration retention of chiral centers. This study provides an environment-friendly, scalable and cost effective protocol to construct value-added cyclic carbonates with multi-functional groups and chiral centers.
- Zhou, Hui,Zhang, Hui,Mu, Sen,Zhang, Wen-Zhen,Ren, Wei-Min,Lu, Xiao-Bing
-
supporting information
p. 6335 - 6341
(2019/12/03)
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- Identifying the components of the solid–electrolyte interphase in Li-ion batteries
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The importance of the solid–electrolyte interphase (SEI) for reversible operation of Li-ion batteries has been well established, but the understanding of its chemistry remains incomplete. The current consensus on the identity of the major organic SEI component is that it consists of lithium ethylene di-carbonate (LEDC), which is thought to have high Li-ion conductivity, but low electronic conductivity (to protect the Li/C electrode). Here, we report on the synthesis and structural and spectroscopic characterizations of authentic LEDC and lithium ethylene mono-carbonate (LEMC). Direct comparisons of the SEI grown on graphite anodes suggest that LEMC, instead of LEDC, is likely to be the major SEI component. Single-crystal X-ray diffraction studies on LEMC and lithium methyl carbonate (LMC) reveal unusual layered structures and Li+ coordination environments. LEMC has Li+ conductivities of >1 × 10?6 S cm?1, while LEDC is almost an ionic insulator. The complex interconversions and equilibria of LMC, LEMC and LEDC in dimethyl sulfoxide solutions are also investigated.
- Wang, Luning,Menakath, Anjali,Han, Fudong,Wang, Yi,Zavalij, Peter Y.,Gaskell, Karen J.,Borodin, Oleg,Iuga, Dinu,Brown, Steven P.,Wang, Chunsheng,Xu, Kang,Eichhorn, Bryan W.
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p. 789 - 796
(2019/08/22)
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- Method for synthesizing cyclic carbonate from urea and diol under catalysis of ionic liquid
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The invention provides a method for synthesizing cyclic carbonate from urea and diol under the catalysis of an ionic liquid. The method is characterized in that the cyclic carbonate is synthesized from the urea and diol under the catalysis of a composite catalyst composed of a metal salt and the imidazole ionic liquid under the conditions of a reaction temperature of 100-200 DEG C, a reaction pressure of 5-500 KPa and a reaction time of 1-10 h. The method has the advantages of cheap and easily available raw materials, high catalysis efficiency of the composite catalyst, mild reaction conditions, simple process flow and high industrial application values.
- -
-
Paragraph 0015-0087; 0100-0121
(2019/09/14)
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- Metal free synthesis of ethylene and propylene carbonate from alkylene halohydrin and CO2 at room temperature
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Herein we describe a metal free and one-pot pathway for the synthesis of industrially important cyclic carbonates such as ethylene carbonate (EC) and propylene carbonates (PC) from molecular CO2 under mild reaction conditions. In the actual synthesis, the alkylene halohydrins such as alkylene chloro- or bromo or iodohydrin and organic superbase, 1,8-diazabicyclo-[5.4.0]-undec-7-ene (DBU) reacted equivalently with CO2 at room temperature. The syntheses of cyclic carbonates were performed in DMSO as a solvent. Both 1,2 and 1,3 halohydrin precursors were converted into cyclic carbonates except 2-bromo- and iodoethanol, which were reacted equivalently with DBU through n-alkylation and formed corresponding n-alkylated DBU salts instead of forming cyclic carbonates. NMR analysis was used to identify the reaction components in the reaction mixture whereas this technique was also helpful in terms of understanding the reaction mechanism of cyclic carbonate formation. The mechanistic study based on the NMR analysis studies confirmed that prior to the formation of cyclic carbonate, a switchable ionic liquid (SIL) formed in situ from alkylene chlorohydrin, DBU and CO2. As a representative study, the synthesis of cyclic carbonates from 1,2 chlorohydrins was demonstrated where the synthesis was carried out using chlorohydrin as a solvent as well as a reagent. In this case, alkylene chlorohydrin as a solvent not only replaced DMSO in the synthesis but also facilitated an efficient separation of the reaction components from the reaction mixture. The EC or PC, [DBUH][Cl] as well as an excess of the alkylene chlorhydrin were separated from each other following solvent extraction and distillation approaches. In this process, with the applied reaction conditions, >90% yields of EC and PC were achieved. Meanwhile, DBU was recovered from in situ formed [DBUH][Cl] by using NaCl saturated alkaline solution. Most importantly here, we developed a metal free, industrially feasible CO2 capture and utilization approach to obtain EC and PC under mild reaction conditions.
- Khokarale, Santosh Govind,Mikkola, Jyri-Pekka
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p. 34023 - 34031
(2019/11/11)
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- CO2 promoted synthesis of unsymmetrical organic carbonate using switchable agents based on DBU and alcohols
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1,8-Diazabicyclo[5.4.0]undec-7-ene (DBU) is an effective nucleophilic catalyst for the transesterification of dimethyl carbonate (DMC) with various alcohols and amines, which afforded unsymmetrical organic carbonate and carbamate. It was observed that the transesterification was accelerated under pressurized CO2 in this work. The activity is very high and the best result (89% conversion with 98% selectivity to unsymmetrical carbonate) was obtained for the DBU/alcohol/DMC/CO2 system. The addition of CO2 to DBU/ethanol generated the DBU cation salt, [DBUH][OCOOCH2CH3], which dissociated more favorably under increasing reaction temperature even under pressurized CO2. The salt could also help to activate DMC by H-bond interaction. The reaction system can be extended easily for the catalytic synthesis of carbamates from amines and DMC. After the reaction, the salt was separated from the reaction mixture and DBU can be recovered by the feasible thermal decomposition, offering a straightforward strategy for the recycling of DBU. On the basis of these results, a plausible mechanism involving the role of both DBU and CO2 has been proposed.
- Gu, Qingwen,Fang, Jian,Xu, Zichen,Ni, Wenxiu,Kong, Kang,Hou, Zhenshan
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p. 13054 - 13064
(2018/08/01)
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- Amino-functionalized pyrazole ion liquid and method for catalytic synthesis of cyclic carbonate by utilizing same
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The invention relates to a method for catalytic synthesis of cyclic carbonate by utilizing amino-functionalized pyrazole ion liquid. The method comprises the following steps: adding the amino-functionalized pyrazole ion liquid and an epoxy compound into a reaction kettle according to a molar ratio of 1:(70 to 500), introducing CO2 till pressure in the reaction kettle is 0.5-3.0MPa, then carrying out constant-temperature and constant-pressure reaction for 0.5-5 hours under the condition that the temperature is 80-130 DEG C, and after the reaction is ended, treating to obtain the cyclic carbonate. The amino-functionalized pyrazole ion liquid has the following structural formula shown in the description, wherein n is equal to 1 or 2, and R is CH3 or C2H5. The method has the advantages of simple synthetic process, high catalyst activity, mild catalytic condition, green and environment-friendly effects, no use of other solvents and cocatalysts, no metal contained in the catalyst, and the like.
- -
-
Paragraph 0021-0022; 0023-0044; 0045-0046
(2018/07/30)
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- Highly efficient conversion of CO2 to cyclic carbonates with a binary catalyst system in a microreactor: Intensification of "electrophile-nucleophile" synergistic effect
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An intensification of the "electrophile-nucleophile" synergistic effect was achieved in a microreactor for the coupling reaction of CO2 and epoxides mediated by the binary Al complex/ternary ammonium salt catalyst system. The microreactor techn
- Li, Ming-Ran,Zhang, Ming-Chao,Yue, Tian-Jun,Lu, Xiao-Bing,Ren, Wei-Min
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p. 39182 - 39186
(2018/11/30)
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- Solventless synthesis of cyclic carbonates by direct utilization of CO2 using nanocrystalline lithium promoted magnesia
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Cyclic carbonates are industrially important chemicals. In this work, an efficient synthesis of cyclic carbonate was achieved by cyclization of epoxide with CO2 using nanocrystalline lithium promoted magnesia (Li-MgO), without using any co-catalyst or solvent. A series of Li-MgO were prepared by gel combustion method and well characterized. Li-MgO forms active F-centers (crystallographic defect) due to the difference in valence state of lithium (Li+) and magnesium (Mg2+) and acts as an active site for CO2 activation. In the synthesis of 4-(chloromethyl)-1,3-dioxolan-2-one from epichlorohydrin, 0.75% (w/w) Li-MgO was the most active catalyst for CO2 fixation into cyclic carbonate with excellent conversion (～98%) and selectivity (100%), at 130 °C and 3 MPa of CO2 pressure. The catalyst showed structural stability and was reused for three cycles without loss of activity. The current synthesis protocol is 100% atom-efficient and thus was extended to a variety of substrates. Langmuir- Hinshelwood-Hougen-Watson (LHHW) type of mechanism was proposed and kinetics studied. Both reactants are strongly adsorbed making the overall reaction zero order with an apparent activation energy of 15.14 kcal/mol.
- Rasal, Kalidas B.,Yadav, Ganapati D.,Koskinen, Rauli,Keiski, Riitta
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p. 200 - 208
(2018/05/25)
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- Application method of catalyst for synthesis of cyclic carbonate on basis of low temperature and normal pressure
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The invention discloses an application method of a catalyst for synthesis of cyclic carbonate on the basis of low temperature and normal pressure, and relates to the field of chemical reaction engineering. The application method of the catalyst for synthesis of the cyclic carbonate on the basis of low temperature and normal pressure comprises the following steps: taking an epoxy compound and carbon dioxide as reactants, wherein a main catalyst is nitrogen-containing heterocycles quaternary ammonium salt, a co-catalyst is inorganic salt, under the condition of zero organic solvent, the reactiontemperature is 25-35 DEG C, the reaction time is 1-48 hours, the reaction pressure is 0.1-0.4 Mpa, and the molar ratio of the reactants to the catalysts is 2000: 1-10: 1; and carrying out cycloaddition reaction on the epoxy compound and carbon dioxide to obtain the cyclic carbonate. Reaction conditions are gentle and friendly, reaction can be carried out at normal temperature and under normal pressure, a process is simple, meanwhile, the nitrogen-containing heterocycles quaternary ammonium salt is used as the main catalyst, is adjustable in structure, good in stability and easy to separate, can be repeatedly used and has unchanged catalytic activity, and the co-catalyst and the main catalyst are low in price and high in activity.
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Paragraph 0037; 0066; 0067
(2018/09/12)
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- Application method of catalysts capable of synthesizing cyclic carbonate under normal temperature and atmosphere
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The invention discloses an application method of catalysts capable of synthesizing cyclic carbonate under normal temperature and atmosphere and relates to the field of chemical reaction engineering. The application method of the catalysts capable of synthesizing cyclic carbonate under the normal temperature and atmosphere includes the steps that an epoxy compound and carbon dioxide are adopted asreactants, a morpholine ionic liquid or ionic liquid crystal is adopted as the main catalyst, and a metal inorganic salt the chemical formula of which is MY is adopted as the auxiliary catalyst, wherein without presence of organic solvents, the reaction temperature is 25-40 DEG C, the reaction time is 1-24 hours, the reaction pressure is 0.1 Mpa, and the molar proportion of the reactants to the catalysts is (100:1)-(10:1); the epoxy compound and carbon dioxide are subjected to a cycloaddition reaction to obtain cyclic carbonate. The reaction conditions are mild and friendly, the reaction can be carried out under the normal temperature and pressure, the technological process is simple, and meanwhile, the morpholine ionic liquid or ionic liquid crystal is adopted as the main catalyst. Prepared cyclic carbonate is adjustable in structure, high in the stability and easy to separate and can be used repeatedly several times without changing the catalytic activity, and the auxiliary catalystand the main catalyst are low in price and high in activity.
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Paragraph 0024; 0025; 0060; 0061
(2018/11/22)
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- Diphenyl Carbonate: A Highly Reactive and Green Carbonyl Source for the Synthesis of Cyclic Carbonates
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A practical, safe, and highly efficient carbonylation system involving a diphenyl carbonate, an organocatalyst, and various diols is presented herein and produces highly valuable cyclic carbonates. In reactions with a wide range of diols, diphenyl carbonate was activated by bicyclic guanidine 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) as a catalyst, which successfully replaced highly toxic and unstable phosgene or its derivatives while maintaining the desired high reactivity. Moreover, this new system can be used to synthesize sterically demanding cyclic carbonates such as tetrasubstituted pinacol carbonates, which are not accessible via other conventional methods.
- Baral, Ek Raj,Lee, Jun Hee,Kim, Jeung Gon
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p. 11768 - 11776
(2018/09/27)
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- The protonated carboxyl imidazole ionic liquid and method for catalytic synthesis of cyclic carbonate method (by machine translation)
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The invention relates to a protonated carboxyl imidazole ionic liquid, having the structural formula shown below: ; In the formula, n=1, 2, 3 or 4, X is Cl, I or Br. The invention also discloses the use of its catalytic process for synthesizing cyclic carbonate: will be protonated carboxyl imidazole ionic liquid and epoxy compound in accordance with the 1:100 - 500 the molar ratio of the added in a reaction kettle, access CO2 To the pressure is 0.5 - 3.0 mpa, then at a temperature of 90 - 130 °C and constant pressure reaction under the condition of 0.5 - 3.0 h, after the reaction is finished after treatment to obtain the cyclic carbonate. The method of the invention mild reaction conditions, catalytic process does not use any organic solvent and the cocatalyst, is an environment-friendly catalytic reaction process. The method of the invention of simple synthesis technology, high reaction activity of the catalyst. (by machine translation)
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Paragraph 0033; 0061; 0062
(2018/07/06)
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- Carbon Dioxide Utilisation for the Synthesis of Unsymmetrical Dialkyl and Cyclic Carbonates Promoted by Basic Ionic Liquids
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An efficient and greener synthesis of unsymmetrical organic carbonates mediated by Hünig's base-appended basic ionic liquids, via carbon dioxide conversion, is described here. These ionic liquids were found to be effective bases for the fixation of carbon dioxide by various alcohols and benzyl bromide, at room temperature. When the alcohol and the halide functionalities are present within the same substrate, the reaction cleanly produces a cyclic carbonate. These functionalised basic ionic liquids were fully recyclable with no loss product yields.
- Goodrich, Peter,Gunaratne, H. Q. Nimal,Jin, Lili,Lei, Yuntao,Seddon, Kenneth R.
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p. 181 - 185
(2018/03/09)
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- A by the process for the direct preparation of cyclic carbonic ester method (by machine translation)
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The invention provides a process for the direct preparation of cyclic carbonic ester by the method, the technical proposal is: olefin, oxidizing agent, nitrate, alkali, water and the organic solvent mixed solvent is added in a reaction kettle, carbon dioxide (CO2 ), The reaction temperature is 60 - 140 °C, the reaction time is 2 - 10h, to obtain the product cyclic carbonate. The invention through one-pot synthesis for preparing cyclic carbonate, the process is simple, mild condition, environmental protection, it has certain industrial application prospect. (by machine translation)
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Paragraph 0020; 0021
(2017/07/21)
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- A pyrazole ionic liquid and utilizing its catalytic process for synthesizing cyclic carbonate (by machine translation)
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The invention relates to a pyrazole ionic liquid, the pyrazole ionic liquid is 1, 2 - diethyl pyrazole Iodized salt, its structural formula as follows: . The invention also discloses the use of the pyrazole ionic liquid catalytic process for synthesizing cyclic carbonate, its to epoxy compound and CO2 As raw materials, the use of pyrazole ionic liquid 1, 2 - diethyl pyrazole Iodized salt as catalyst, in pressure 0.5 - 5 mpa, temperature 90 °C -150 °C reaction under the condition of 1 - 5 H-synthesizing cyclic carbonate. The method of the invention the process is simple, mild reaction conditions, the activity of the catalyst is high and is in a solid state at room temperature, has overcome the traditional ion liquid great increase of viscosity of the difficult problem of use, is an environment-friendly catalytic process, the obtained cyclic carbonate the highest yield is 96.2%. (by machine translation)
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Paragraph 0016; 0017; 0018; 0019; 0020-0035; 0036-0037
(2017/08/30)
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- Protonated pyrazole ionic liquid, and method used for catalytic synthesis of cyclic carbonate with protonated pyrazole ionic liquid
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The invention provides a protonated pyrazole ionic liquid, and a method used for catalytic synthesis of cyclic carbonate with the protonated pyrazole ionic liquid. The structure formula of the protonated pyrazole ionic liquid is disclosed in the invention. According to the method, the protonated pyrazole ionic liquid and an epoxy compound are introduced into a high temperature reaction kettle at a molar ratio of 1:10-300, CO2 is introduced into the high temperature reaction kettle until the pressure in the high temperature reaction kettle is increased to 1 to 4MPa, constant temperature constant pressure reaction is carried out for 1 to 4h at 100 to 150 DEG C, and cyclic carbonate is obtained via post-treatment. Compared with the prior art, the method possesses following advantages: reaction conditions are mild, catalyst activity is high, no organic solvent is used in the process, and the catalysis reaction process is friendly to the environment.
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Paragraph 0038; 0043; 0045-0047; 0049; 0051; 0053; 0055
(2017/08/30)
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- Highly Efficient and Convenient Supported Ionic Liquid TiCl5-DMIL@SiO2@Fe3O4-Catalyzed Cycloaddition of CO2 and Epoxides to Cyclic Carbonates
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Abstract: A series of silica coated magnetic nanoparticles supported ILs were prepared, characterized and their catalytic performances in cycloaddition of CO2 to epoxides were investigated. The influences of various reaction parameters including catalyst selection, catalyst amount, reaction time, and reaction temperature were studied. Research shows that TiCl5-DMIL@SiO2@Fe3O4 could be used as the highest efficient catalyst in cycloaddition of CO2 and epoxides to gives the corresponding cyclic carbonates. Good to excellent yields were achieved for this reaction under mild conditions. The heterogeneous supported catalyst is easily recoverable by filtration, and could be used for five consecutive runs without significant loss in catalytic activity.
- Hu, Yu Lin,Xing, Rong
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p. 1453 - 1463
(2017/05/16)
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- For the preparation of a quaternary phosphonium salt catalyst preparation of cyclic carbonic ester method
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The invention relates to a method for preparing cyclic carbonate by using a supported quaternary phosphonium salt catalyst, which comprises the following step: by using a supported quaternary phosphonium salt as the catalyst which accounts for 0.2-5 mol%
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Paragraph 0020; 0055-0057
(2018/01/13)
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- Protonated alkylpyrazole ionic liquid and method using same for synthesizing cyclic carbonate
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The invention relates to protonated alkylpyrazole ionic liquid with a structural formula as shown in the description, wherein n is equal to 1, 2, 3 or 4, and X is Cl, Br or I. The invention further discloses a method for synthesizing cyclic carbonate by using the protonated alkylpyrazole ionic liquid; the protonated alkylpyrazole ionic liquid and an epoxy compound are added into a high-pressure reaction kettle according to a molar ratio of 1 : (25 to 300), CO2 is introduced until pressure is 1-3 MPa, and constant-temperature constant-pressure reaction is performed for 1-5 hours at a temperature of 100-150 DEG C, and post-treatment is performed after reaction is ended, thus obtaining the cyclic carbonate. The method solves the problems that CO2 activation is difficulty, a catalyst is dear, a poisonous organic solvent is used, a synthesis process is complex, reaction conditions are harsh and the like in an existing method. The advantages of simple synthesis process, high catalyst activity, environmental friendliness, low cost and the like are achieved.
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Paragraph 0038; 0064; 0083; 0084; 0085; 0086
(2018/01/12)
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- Method for synthesizing carbonic ester by using carbon dioxide at ordinary pressure
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The invention discloses a method for synthesizing carbonic ester by using carbon dioxide at ordinary pressure. According to the method, the carbon dioxide is continuously introduced in a reaction system in the reaction process, constant ordinary pressure is maintained by the system, and reaction is conducted in a non-pressure resistance reactor. Lewis acid and quaternary ammonium salt are adopted by the method to form a co-catalysis system, a catalyst is cheap and easy to obtain, the operation is simple, the reaction condition is mild, and the catalytic activity is high. In an optimized reaction condition, i.e., in the ordinary pressure, reaction is conducted for 3h at 100 DEG C, the yield of cyclic carbonate is 69.5-90.2%, and the yield of diphenyl carbonate is 8.6%. The method has the advantages that the reaction can be efficiently conducted in a common non-pressure resistance reactor, the operation is safe, and the large-scale industrial production is favorably realized.
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Paragraph 0023
(2018/04/01)
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- Dialkylpyrazolium ionic liquids as novel catalyst for efficient fixation of CO2 with metal- and solvent-free
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The efficient fixation of CO2 without co-catalyst and solvent under metal-free condition is still an urgent topic in sustainable chemistry. In this work, a series of dialkylpyrazolium ionic liquids are employed to promote the cycloaddition of CO2 and PO to produce PC. They would be easily synthesized by a simple one-pot reaction. The effect of alkyl chain length in cation and different anion is explored. Diethylpyrazolium iodide presents the excellent catalytic activity with the product yield of 96% and selectivity of 99% in a benign condition. Moreover, the catalyst could be reused for at least five times without significant loss of catalytic activity. An intensive structure-activity research testifies that the cycloaddition of CO2 with PO is activated by a synergistic effect from both cation and anion of ILs. To confirm it, the detailed mechanism is investigated by density functional theory associated with the non-covalent interactions and atoms in molecule analysis. Besides the electrostatic interaction between cation of ionic liquid and PO, the noncovalent interaction, especially for hydrogen bond, plays a vital role in promoting the reaction.
- Ma, Yuan,Chen, Ci,Wang, Tengfei,Zhang, Jingshun,Wu, JiaJia,Liu, Xiangdong,Ren, Tiegang,Wang, Li,Zhang, Jinglai
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p. 265 - 273
(2017/09/19)
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