- Highly Efficient Fixation of Carbon Dioxide at RT and Atmospheric Pressure Conditions: Influence of Polar Functionality on Selective Capture and Conversion of CO2
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The rapid increase in the concentration of atmospheric carbon dioxide (CO2) has resulted in undesirable environmental issues. Hence, selective CO2 capture and utilization as C1 feedstock for the preparation of high-value chemicals and fuels has been considered as a promising step toward mitigating the growing concentration of atmospheric CO2. In this direction, herein we report rational construction of a Ag(I)-anchored sulfonate-functionalized UiO-66 MOF named as MOF-SO3Ag composed of CO2-philic sulfonate functionality and catalytically active alkynophilic Ag(I) sites for chemical fixation of carbon dioxide. The MOF-SO3Ag exhibits selective as well as recyclable adsorption of CO2 with a high heat of adsorption energy (Qst) of 37.8 kJ/mol. On the other hand, the analogous MOF, UiO-66 doped with Ag(I), showed a lower Qst value of 30 kJ/mol, highlighting the importance of the sulfonate group for stronger interaction with CO2. Furthermore, the MOF-SO3Ag acts as an efficient heterogeneous catalyst for cyclic carboxylation of propargylic alcohols to generate α-alkylidene cyclic carbonates in >99percent yield at mild conditions of RT and 1 bar CO2. More importantly, one-pot synthesis of oxazolidinones by a three-component reaction between CO2, propargylic alcohol, and primary amine has also been achieved using MOF-SO3Ag catalyst under the mild conditions. The MOF is highly recyclable and retains its superior catalytic activity even after several cycles. To the best of our knowledge, MOF-SO3Ag is the first example of MOF reported for RT chemical fixation of CO2 to oxazolidinones by aminolysis of α-alkylidene cyclic carbonates under the environment-friendly mild conditions.
- Das, Rajesh,Nagaraja, C. M.
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- Copper(i) iodide cluster-based lanthanide organic frameworks: Synthesis and application as efficient catalysts for carboxylative cyclization of propargyl alcohols with CO2 under mild conditions
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Two metal-organic frameworks (MOFs), namely, [Dy2Cu4I4(NA)6(DMF)2]n (1) and [Gd2Cu2I2(IN)6(DMF)4]·5DMF (2) (HNA = nicotinic acid, HIN = isonicotinic acid), constructed based on lanthanide ions and copper iodide clusters ([Cu4I4] and [Cu2I2]) were successfully synthesized and characterized. Compound 1 has a three-dimensional framework and compound 2 displays a two-dimensional plane with sql topology, respectively. Both of them exhibit high thermostability and solvent stabilities. Additionally, catalytic explorations reveal that 1 displays higher catalytic activity than 2 for the carboxylic cyclization of propargyl alcohols. More importantly, 1 also exhibits excellent catalytic performance in the carboxylation reactions of CO2 and terminal propargylic alcohols with various substituents. To the best of our knowledge, this is the first example of non-noble metal based MOF catalysts for the carboxylative cyclization of propargyl alcohols with CO2 under atmospheric pressure and at room temperature, which provides a highly promising approach for MOFs in the catalytic conversion of CO2 to valuable chemicals.
- Bai, Guoyi,Lan, Xingwang,Li, Meng,Wu, Zhilei,Zhang, Yaxin
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- A simple and robust AgI/KOAc catalytic system for the carboxylative assembly of propargyl alcohols and carbon dioxide at atmospheric pressure
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A simple and robust AgI/KOAc system was developed for the cyclization of propargyl alcohols and carbon dioxide under mild conditions, and was identified to have excellent activities for numerous substrates, especially sterically hindered terminal alkynes and internal alkynes. Notably, the Ag loading involved was an unprecedentedly low level of 0.05 mol%.
- Yuan, Ye,Xie, Yu,Zeng, Cheng,Song, Dandan,Chaemchuen, Somboon,Chen, Cheng,Verpoort, Francis
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- A rose bengal-functionalized porous organic polymer for carboxylative cyclization of propargyl alcohols with CO2
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A Rose bengal-functionalized porous organic polymer (RB-POP) was prepared with a specific surface area of up to 562 m2 g-1. In the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene, RB-POP supported Ag(0) nanoparticles exhibited excellent performance for catalyzing cyclization of propargyl alcohols with CO2 at 30 °C, achieving a TOF of 5000 h-1, the highest value among the reported ones.
- Yu, Xiaoxiao,Yang, Zhenzhen,Zhang, Fengtao,Liu, Zhenghui,Yang, Peng,Zhang, Hongye,Yu, Bo,Zhao, Yanfei,Liu, Zhimin
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- A recyclable AgI/OAc- catalytic system for the efficient synthesis of α-alkylidene cyclic carbonates: Carbon dioxide conversion at atmospheric pressure
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The cyclization of carbon dioxide and propargylic alcohols, especially challenging substrates, were efficiently catalyzed by a green and recyclable AgI/OAc- system under atmospheric pressure, which is shown to be the most recyclable system with 20 recycle rounds and has the lowest loading among all the reported recyclable systems that work under atmospheric pressure.
- Yuan, Ye,Xie, Yu,Zeng, Cheng,Song, Dandan,Chaemchuen, Somboon,Chen, Cheng,Verpoort, Francis
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- Synthesizing Ag Nanoparticles of Small Size on a Hierarchical Porosity Support for the Carboxylative Cyclization of Propargyl Alcohols with CO2 under Ambient Conditions
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Both immobilization of Ag nanoparticles (AgNPs) of very small size on hierarchical porosity supports and carboxylative cyclization of propargyl alcohols with CO2 under ambient conditions are very interesting. In this work, we synthesized AgNPs supported on sulfonated macroreticular resin (SMR) with hierarchical pores in water/alcohol solutions. It was shown that the size of the AgNPs on the SMR could be tailored easily by altering the synthetic solutions, and very small AgNPs with narrow size distribution (1-3 nm) could be obtained in water/methanol solution. It was found that the AgNPs/SMR with small AgNPs was highly efficient and an easily recyclable catalyst for the synthesis of α-alkylidene cyclic carbonates by carboxylative cyclization of propargyl alcohols with CO2 at ambient pressure and temperature, which was the first work to use metal nanoparticles as the catalysts for the reaction.
- Cui, Meng,Qian, Qingli,He, Zhenhong,Ma, Jun,Kang, Xinchen,Hu, Jiayin,Liu, Zhimin,Han, Buxing
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- A dual-functional urea-linked conjugated porous polymer anchoring silver nanoparticles for highly efficient CO2conversion under mild conditions
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A dual-functional urea-linked conjugated porous polymer (UCPP) assembled by enol-imine with ordered unit arrays that act as potential anchoring sites in the networks was fabricated, and was further applied as a support for Ag nanoparticles by the coordinate interaction between them. The UCPP not only can well confine the Ag particle size and facilitate high dispersion, but also can afford special CO2-philic moieties to enhance the adsorption properties. The resulting Ag?UCPP as a heterogeneous catalyst exhibited excellent activity for the carboxylative cyclization of propargyl alcohols with CO2 under mild conditions, together with good recyclability, which is probably attributed to the synergistic effect of the UCPP on the adsorption and activation of CO2 and the immobilization of Ag nanoparticles. This work affords possible opportunities for the design and synthesis of a heterogeneous catalyst toward CO2 conversion.
- Li, Lin,Li, Wang,Li, Yuting,Liu, Xiaozhen,Wang, Jianxin,Wang, Liping,Wang, Xiaoji,Zhu, Jie
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- Unusual Missing Linkers in an Organosulfonate-Based Primitive-Cubic (pcu)-Type Metal-Organic Framework for CO2 Capture and Conversion under Ambient Conditions
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A noninterpenetrated organosulfonate-based metal-organic framework (MOF) with a defective primitive-cubic (pcu) topology was successfully synthesized. The unusual missing linkers, along with the highest permanent porosity (~43%) in sulfonate-MOFs, offer a versatile platform for the incorporation of alkynophilic Ag(I) sites. The cyclic carboxylation of alkyne molecules (e.g., propargyl alcohol and propargyl amine) into α-alkylidene cyclic carbonates and oxazolidinones were successfully catalyzed by the use of Ag(I)-embedded sulfonate-MOF under atmospheric pressure of CO2. In all the three catalytic reactions using CO2 as a C1 feedstock, the highly robust sulfonate-based MOF catalyst exhibit at least three-cycle reusability.
- Zhang, Guiyang,Yang, Huimin,Fei, Honghan
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- Tetrabutylphosphonium-Based Ionic Liquid Catalyzed CO2 Transformation at Ambient Conditions: A Case of Synthesis of α-Alkylidene Cyclic Carbonates
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A series of tetrabutylphosphonium ([Bu4P]+)-based ionic liquids (ILs) with multiple-site for CO2 capture and activation in their anions, which could efficiently catalyze the cyclization reaction of propargylic alcohols with CO2 at ambient conditions, are reported. Especially, the IL, [Bu4P]3[2,4-OPym-5-Ac], which has three interaction sites for attracting CO2 together with a pKa1 value of 9.13, exhibited the best performance, affording a series of α-alkylidene cyclic carbonates in moderate to good yields. The mechanism exploration demonstrated that IL served as a bifunctional catalyst with anion simultaneously activating CO2 via multiple-site cooperative interactions and the C≡C triple bond in propargylic alcohol via inductive effect, thus resulting in the production of α-alkylidene cyclic carbonates. (Chemical Equation Presented).
- Wu, Yunyan,Zhao, Yanfei,Li, Ruipeng,Yu, Bo,Chen, Yu,Liu, Xinwei,Wu, Cailing,Luo, Xiaoying,Liu, Zhimin
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- Solvent-Dependent Assembly and Magnetic Relaxation Behaviors of [Cu4I3] Cluster-Based Lanthanide MOFs: Acting as Efficient Catalysts for Carbon Dioxide Conversion with Propargylic Alcohols
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Two structurally similar metal-organic frameworks (MOFs) [Dy2Cu4I3(IN)7(DMF)2]·DMF (1) and [Dy2Cu4I3(IN)7(DMA)2]·DMA (2) (HIN = isonicotinic acid) feathering different coordinated solvent molecules were successfully isolated by tuning the types of solvents in the reaction system. Structural tests indicate that 1 and 2 are both built from 1D Dy(III) chains and copper iodide clusters [Cu4I3], generating into three-dimensional frameworks with an open 1D channel along the a axis. 1 and 2 display extensive and excellent solvent stability. Magnetic studies of 1 and 2 indicate that they exhibit interesting solvent-dependent magnetization dynamics. Importantly, 1 and 2 can act as highly effective catalysts for the carboxylic cyclization of propargyl alcohols with carbon dioxide (CO2) under ambient operating conditions. Additionally, the substrate scope was further explored over compound 1 based on the optimal conditions, and it exhibits efficient cyclic carboxylation of various terminal propargylic alcohols with CO2. This research offers an effective approach for the solvent-guided synthesis of MOFs materials and also presents the great application value of MOFs in CO2 chemical conversion.
- Wu, Zhi-Lei,Gu, Ai-Ling,Gao, Ning,Cui, Hui-Ya,Wang, Wen-Min,Cui, Jian-Zhong
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- A Noble-Metal-Free Metal–Organic Framework (MOF) Catalyst for the Highly Efficient Conversion of CO2 with Propargylic Alcohols
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Cyclization of propargylic alcohols with CO2 is an important reaction in industry, and noble-metal catalysts are often employed to ensure the high product yields under environmentally friendly conditions. Herein a porous noble-metal-free framework 1 with large 1D channels of 1.66 nm diameter was synthesized for this reaction. Compound 1 exhibits excellent acid/base stability, and is even stable in corrosive triethylamine for one month. Catalytic studies indicate that 1 is an effective catalyst for the cyclization of propargylic alcohols and CO2 without any solvents under mild conditions, and the turnover number (TON) can reach to a record value of 14 400. Furthermore, this MOF catalyst also has rarely seen catalytic activity when the biological macromolecule ethisterone was used as a substrate. Mechanistic studies reveal that the synergistic catalytic effect between CuI and InIII plays a key role in the conversion of CO2.
- Hou, Sheng-Li,Dong, Jie,Jiang, Xiao-Lei,Jiao, Zhuo-Hao,Zhao, Bin
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- Azole-Anion-Based Aprotic Ionic Liquids: Functional Solvents for Atmospheric CO2 Transformation into Various Heterocyclic Compounds
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The chemical transformation of atmospheric CO2 is of great significance yet still poses a great challenge. Herein, azole-anion-based aprotic ionic liquids (ILs) were synthesized by the deprotonation of weak proton donors (e.g., 2-methylimidazole, 4-methylimidazole, and 2,4-dimethylimidazole) with tetrabutylphosphonium hydroxide, [Bu4P][OH]. We found that these ILs, such as [Bu4P][2-MIm], could activate atmospheric CO2 through the formation of carbamates. The resultant carbamate intermediates could further react with various types of substrate, including propargylic alcohols, 2-aminobenzonitriles, ortho-phenylenediamines, and 2-aminothiophenol, thereby producing α-alkylidene cyclic carbonates, quinazoline-2,4(1 H,3 H)-diones, benzimidazolones, and benzothiazoline, respectively, in moderate-to-good yields. Thus, we have achieved the transformation of CO2 at atmospheric pressure, and we expect this method to open up new routes for the synthesis of various oxygen-containing heterocyclic compounds under metal-free conditions.
- Zhao, Yanfei,Wu, Yunyan,Yuan, Guangfeng,Hao, Leiduan,Gao, Xiang,Yang, Zhenzhen,Yu, Bo,Zhang, Hongye,Liu, Zhimin
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- Synthesis of α-alkylidene cyclic carbonatesviaCO2fixation under ambient conditions promoted by an easily available silver carbamate
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The simple and cost-effective compound [Ag(O2CNEt2)], in combination with PPh3, works as an effective catalytic precursor in the carboxylation of propargyl alcohols at ambient temperature and atmospheric CO2pressure, and in most cases under solventless conditions. The silver carbamate revealed a better performance than commercial silver oxide, Ag2O, and allowed to obtain a series of α-alkylidene cyclic carbonates in high yields.
- Bresciani, Giulio,Bortoluzzi, Marco,Ghelarducci, Claudia,Marchetti, Fabio,Pampaloni, Guido
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- Polystyrene-supported N-heterocyclic carbene-silver complexes as robust and efficient catalysts for the reaction of carbon dioxide and propargylic alcohols
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Three polystyrene-supported N-heterocyclic carbene-silver complexes [PS-NHC-Ag(I)] and a polystyrene-supported N-heterocyclic carbene-copper complex [PS-NHC-Cu(I)] catalyst were synthesized and characterized by elemental analysis, Fourier transform infrared spectroscopy, inductively coupled plasma-atom emission spectrometer, thermogravimetric analysis and scanning electron micrographs. The catalytic activity of the supported catalysts was investigated for the reaction of propargylic alcohols and carbon dioxide. PS-NHC-Cu(I) showed no catalytic activity to the reaction, while PS-NHC-Ag(I) showed a considerable high activity and selectivity for the reaction, yielding the corresponding α-alkylidene cyclic carbonates in high to excellent yields under mild conditions. Most importantly, the supported catalysts could be separated easily from the products and reused up to 15 times without loss of their high catalytic activity, showing excellent stability. The effect of various reaction parameters such as carbon dioxide pressure, temperature, time, and catalyst loading on the reaction was also investigated. Copyright
- Tang, Xiaodong,Qi, Chaorong,He, Haitao,Jiang, Huanfeng,Ren, Yanwei,Yuan, Gaoqing
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- One-pot carboxylative cyclization of propargylic alcohols and CO2 catalysed by N-heterocyclic carbene/Ag systems
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A series of N-heterocyclic carbene (NHC)/Ag systems were developed for the carboxylative assembly of propargylic alcohols and carbon dioxide (CO2). With the catalysis of these catalytic systems, a variety of target α-alkylidene cyclic carbonates could be obtained smoothly under atmospheric CO2 pressure in straightforward one-pot processes. Particularly, these reactions could be performed without any stoichiometric addition of bases or additives. Further mechanistic investigation reveals that the excellent activities are attributed to the effective activations of CO2 accomplished by the NHCs via the formation of the NHC-CO2 adducts.
- Yuan, Ye,Xie, Yu,Song, Dandan,Zeng, Cheng,Chaemchuen, Somboon,Chen, Cheng,Verpoort, Francis
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- Copper-catalysed synthesis of α-alkylidene cyclic carbonates from propargylic alcohols and CO2
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We report a N-heterocyclic carbene copper(i) complex-catalysed formal cycloaddition between readily available propargylic alcohols and carbon dioxide at room temperature. By using the combination of a sterically demandingBPDPrCuCl complex (BPDPr = 1,3-bis(2,6-diisopropylphenyl)-1,3-diazonine-2-ylidene) and CsF, as catalytic system, primary propargylic alcohols are efficiently converted to the corresponding α-alkylidene cyclic carbonates. Gram scale (up to 89% yield) and reusability experiments (74% global yield, turnover number value = 103) showcase the robustness of the catalytic system. This practically simple protocol also tolerates secondary and tertiary propargylic alcohols under CO2at atmospheric pressure, enabling the direct synthesis of substituted and unsubstituted α-alkylidene cyclic carbonates at room temperature.
- Cervantes-Reyes, Alejandro,Farshadfar, Kaveh,Rudolph, Matthias,Rominger, Frank,Schaub, Thomas,Ariafard, Alireza,Hashmi
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supporting information
p. 889 - 897
(2021/02/09)
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- Noble metal-free Cu(i)-anchored NHC-based MOF for highly recyclable fixation of CO2under RT and atmospheric pressure conditions
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The utilization of CO2as a C1 feedstock for the synthesis of high-value chemicals and fuels is an important step towards mitigating the increasing concentration of atmospheric carbon dioxide as well as the production of value-added chemicals. Herein, we demonstrate the development of an efficient recyclable catalyst for the conversion of CO2into oxazolidinones, which are important commodity chemicals for antibiotics, by utilizing an N-heterocyclic carbene (NHC)-based metal-organic framework (MOF). The NHC-centers lined in the pore walls of the MOF were utilized to anchor catalytically active Cu(i) ions by post-synthetic modification (PSM). The Cu(i)-embedded MOF showed highly recyclable and selective CO2uptake properties with a high heat of interaction energy of 43 kJ mol?1. The presence of a high density of CO2-philic NHC and catalytic Cu(i) sites in the 1D channels of the MOF render highly efficient catalytic activity for fixation of CO2into α-alkylidene cyclic carbonates and oxazolidinones at RT and atmospheric pressure conditions. Notably, Cu(i)@NHC-MOF showed excellent recyclability for up to 10 cycles of regeneration with retention of catalytic activity as well as chemical stability. To the best of our knowledge, Cu(i)@NHC-MOF is the first example of a noble metal-free MOF-based heterogeneous catalyst for the utilization of CO2to synthesize important value-added chemicals under mild conditions.
- Das, Rajesh,Nagaraja, C. M.
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supporting information
p. 5195 - 5204
(2021/07/29)
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- Tubular metal organic frameworks from the curvature of 2D-honeycombed metal coordination
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A tubular MOF with adequate active sites is prepared by the bending of metal-coordinated honeycombed frameworks via titration and shows fast catalytic kinetics with lower catalytic loading for CO2 conversion. The TON is observed to be 2300 and the corresponding TOF of up to 173 h-1 is achieved for the first time.
- Bao, Junhui,Chen, Yaju,Huang, Liping,Huang, Zhegang,Ji, Hongbing,Kim, Jehan,Wu, Shanshan,Xu, Xin,Zhang, Liwei,Zhou, Xiantai
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supporting information
p. 2403 - 2406
(2020/03/05)
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- A novel crystalline azine-linked three-dimensional covalent organic framework for CO2 capture and conversion
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The targeted synthesis of three-dimensional covalent organic frameworks (3D COFs) is a great challenge, especially those synthesized by using a new kind of organic linkage. Herein, for the first time, a novel 3D azine-linked COF (3D-HNU5) has been synthesized and characterized. It is shown that the obtained 3D COF has a 2-fold interpenetrated diamond topology, and shows good chemical/thermal stability and a narrow pore size distribution, which exhibits excellent performance in the selective uptake of CO2 over N2. Moreover, the 3D-HNU5 is found to be an efficient catalyst for the cycloaddition of propargylic alcohols with CO2 into carbonates with excellent catalytic activity under mild conditions.
- Guan, Pengxin,Qiu, Jikuan,Zhao, Yuling,Wang, Huiyong,Li, Zhiyong,Shi, Yunlei,Wang, Jianji
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supporting information
p. 12459 - 12462
(2019/10/23)
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- Method for preparing unsaturated cyclic carbonate by using carbon dioxide as raw material
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The invention discloses a method for preparing unsaturated cyclic carbonate. The method comprises the step of performing a catalytic reaction on alkynol and CO2 in a reactor in the presence of sulfonic acid resin loaded silver nano-particles, an alkali promoter and a solvent to obtain unsaturated cyclic carbonate. According to the method, a silver nano-particle catalyst with uniform granularity and high dispersion in the sulfonic acid resin loaded silver nano-particles is utilized for the first time, the catalytic system formed by the catalyst, the alkali promoter and the solvent is utilized, and carbon dioxide and alkynol serving as raw materials are used for preparing unsaturated cyclic carbonate at normal temperature and normal pressure. The preparation method is simple. The catalyst has excellent activity, stability and recycling performance, and has a great application value.
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Paragraph 0066-0082; 0088
(2017/08/28)
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- AgX@carbon (X = Br and I) as robust and efficient catalysts for the reaction of propargylic alcohols and CO2 to carbonates under ambient conditions
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Development of new efficient catalytic systems for chemical transformation of CO2 is a very attractive topic in green chemistry. In this work, we studied the synthesis of α-alkylidene cyclic carbonates through the coupling reaction between propargylic alcohols and CO2 with new silver catalysts. It was found that activated carbon supported AgX (X = Br and I) was a simple and efficient catalyst for the carboxylative cyclization of propargyl alcohols with CO2 at atmospheric pressure and room temperature. Nearly 99% yield of the desired product was obtained, and the product could be simply separated through solvent extraction. Moreover, the catalyst could be easily recovered and reused at least ten times without a decrease in the catalytic activity and selectivity. These findings are useful for the development of an environmentally friendly chemical process for the production of α-alkylidene cyclic carbonates.
- Qiu, Jikuan,Zhao, Yuling,Wang, Huiyong,Cui, Guokai,Wang, Jianji
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p. 54020 - 54026
(2016/07/06)
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- Zinc(II)-catalyzed reactions of carbon dioxide and propargylic alcohols to carbonates at room temperature
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Carbon dioxide (CO2) is an abundant and renewable feedstock for the production of value-added chemicals. Herein, we carried out the first work to use ZnI2/NEt3 as the catalyst for the reactions of CO2 and propargylic alcohols to form α-alkylidene cyclic carbonates. It was discovered that the catalyst system could efficiently promote the reaction at room temperature under solvent-free conditions, and the yields of the target products could reach 99%. The zinc(ii) and NEt3 play excellent synergistic roles in activating both CO2 and propargylic alcohols.
- Hu, Jiayin,Ma, Jun,Zhu, Qinggong,Qian, Qingli,Han, Hongling,Mei, Qingqing,Han, Buxing
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supporting information
p. 382 - 385
(2016/01/30)
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- Alkoxide-functionalized imidazolium betaines for CO2 activation and catalytic transformation
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Alkoxide-functionalized imidazolium betaines (AFIBs), including an alkoxide anion and an imidazolium cation, were synthesized by treating potassium tert-butoxide with 1-(2-hydroxyethyl)-2,3-disubstituted imidazolium bromide. The novel betaines were able to quickly capture CO2, affording carboxylate zwitterions (AFIB-CO2 adducts). In the presence of adventitious water, the transformation of the AFIB-CO2 adducts into the corresponding bicarbonate salts was observed by 1H and 13C NMR spectroscopy. The structures of the AFIB bicarbonate salts were solved using single crystal X-ray crystallography. Furthermore, the dithiocarboxylate zwitterions (AFIB-CS2 adducts), which are more stable to moisture in comparison with their CO2 adducts, were prepared by reacting CS2 with the corresponding betaines. X-Ray single crystal analysis revealed the bent geometry of the binding CS2 in the dithiocarboxylate zwitterions with a S-C-S angle of 126.6-126.9°, which indirectly confirms the structures of the AFIB-CO2 adducts in hand. These AFIB-CO2 adducts were found to function as organocatalysts for the coupling reaction of propargylic alcohols with CO 2 for selectively producing valuable cyclic carbonates under mild and solvent-free reaction conditions. the Partner Organisations 2014.
- Wang, Yan-Bo,Sun, Dong-Sheng,Zhou, Hui,Zhang, Wen-Zhen,Lu, Xiao-Bing
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p. 2266 - 2272
(2014/04/17)
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- Process for manufacturing cyclocarbonates using a silver salt catalyst
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A process for the manufacture of 4,4-disubstituted 5-methylene-1,3-dioxolan-2-ones ("cyclocarbonates") of the formula: STR1 wherein R1 and R2 each independently signify a saturated or olefinically-unsaturated aliphatic group or an aromatic group, or R1 and R2 together form tetra- or pentamethylene, by reacting a corresponding 3,3-disubstituted prop-1-yn-3-ol of the formula HC C--C(R1)(R2)--OH (II) with carbon dioxide in the presence of a quaternary ammonium or phosphonium salt as the catalyst comprises using a silver salt as a further catalyst. An alkali metal or quaternary ammonium or phosphonium salt of a carboxylic acid can also be used to increase the catalytic performance of the silver salt catalyst. Moreover, the addition of triphenylphosphine serves to accelerate the reaction to some extent. The silver salts catalyze this process significantly better than the previously utilized copper salts. Advantageously, the process uses much smaller amounts of catalyst, significantly shortens reaction times, and mandates less drastic reaction conditions. Cyclocarbonates produced by this process are valuable intermediates for the production of polymerizates and other useful substances, such as dyestuffs and carotenoids.
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- Cobaltocene-Catalyzed Reaction of Carbon Dioxide with Propargyl Alcohols
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The reaction of carbon dioxide with α-ethynyl tertiary alcohols has been catalyzed by cobaltocene to give α-methylene cyclic carbonates in good yields. α-Ethynyl primary or secondary alcohols give noncyclic alkyl carbonates in fair yields.
- Inoue, Yoshio,Ishikawa, Jiro,Taniguchi, Masaaki,Hashimoto, Harukichi
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p. 1204 - 1206
(2007/10/02)
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