66675-43-2Relevant academic research and scientific papers
Synthesis of cyclic carbonate from carbon dioxide and epoxide using amino acid ionic liquid under 1atm pressure
Gong, Qing,Luo, Huadong,Cao, Jin,Shang, Yuhan,Zhang, Haibo,Wang, Wenjing,Zhou, Xiaohai
, p. 381 - 386 (2012)
Herein, we report an effective synthesis of cyclic carbonates by cycloaddition of carbon dioxide to epoxide using a modified amino acid ionic liquid as catalyst under 1atm pressure. With triethylamine as co-catalyst, the catalytic activity of the l-proline based ionic liquid was greatly enhanced, and up to 97% isolated yield of cyclic carbonate was achieved at 90C under atmospheric pressure without organic solvent and metal component.
Synthesis of Cyclohexene Carbonate Catalyzed by Polymer-Supported Catalysts
Cui, Ke,Liang, Zhengyong,Zhang, Jing,Zhang, Yadong
, p. 712 - 723 (2015)
A series of polystyrene-divinylbenzene cross-linked resin (PS)-supported zinc chloride catalysts were prepared in this study. They can efficiently catalyze the solventless cycloaddition of cyclohexene oxide with carbon dioxide in the presence of tetrabutylammonium bromide (TBAB) as cocatalyst under relatively mild reaction conditions. The catalyst is composed of carrier, connecting arm, ligand, and active ingredient. The connecting arms of different lengths can significantly affect the catalytic activity. Among these catalysts, the one using diethylene glycol as connecting arm and 2-aminopyridine as ligand, named PS-DEG-2ap-ZnCl2, showed the optimal catalytic performance. The yield of cyclohexene carbonate was 95.18% calculated by gas chromatographic analysis under the optimal conditions (393 K, 5 MPa, 6 h). Moreover, the catalyst showed good stability and reusability. From the viewpoint of industrial application, the catalyst is attractive because of its excellent catalytic efficiency on the synthesis of cyclohexene carbonate. GRAPHICAL ABSTRACT.
Diethylene Glycol/NaBr Catalyzed CO2 Insertion into Terminal Epoxides: From Batch to Continuous Flow
Rigo, Davide,Calmanti, Roberto,Perosa, Alvise,Selva, Maurizio,Fiorani, Giulia
, p. 2005 - 2016 (2021/02/27)
CO2 insertion reactions on terminal epoxides (styrene oxide, 1,2-epoxyhexane and butyl glycidyl ether) were performed in a binary homogeneous mixture comprising NaBr as the nucleophilic catalyst and diethylene glycol (DEG) as both solvent and catalyst activator (cation coordinating agent). The reaction protocol was initially studied under batch conditions either in autoclaves and glass reactors: quantitative formation of the cyclic organic carbonate products (COCs) were achieved at T=100 °C and p0(CO2)=1–40 bar. The process was then transferred to continuous-flow (CF) mode. The effects of the reaction parameters (T, p(CO2), catalyst loading, and flow rates) were studied using microfluidic reactors of capacities variable from 7.85 ? 10?2 to 0.157 cm3. Albeit the CF reaction took place at T=220 °C and 120 bar, CF improved the productivity and allowed catalyst recycle through a semi-continuous extraction procedure. For the model case of 1,2-epoxyhexane, the (non-optimized) rate of formation of the corresponding carbonate, 4-butyl-1,3-dioxolan-2-one, was increased up to 27.6 mmol h?1 equiv.?1, a value 2.5 higher than in the batch mode. Moreover, the NaBr/DEG mixture was reusable without loss of performance for at least 4 subsequent CF-tests.
Direct oxidative carboxylation of terminal olefins to cyclic carbonates by tungstate assisted-tandem catalysis
Calmanti, Roberto,Perosa, Alvise,Selva, Maurizio
, p. 7609 - 7619 (2021/10/12)
Tungstate catalysts are well established for olefin epoxidation reactions, while their catalytic activity for CO2 insertion in epoxides is a more recent discovery. This dual reactivity of tungstate prompted the present development of a catalytic tandem process for the direct conversion of olefins into the corresponding cyclic organic carbonates (COCs). Each of the two steps was studied in the presence of the ammonium tungstate ionic liquid catalyst-[N8,8,8,1]2[WO4]-obtained via a benign procedure starting from ammonium methylcarbonate ionic liquids. The catalytic epoxidation first step was optimised on 1-decene as model substrate, using H2O2 as benign oxidant, [N8,8,8,1]2[WO4] as catalyst and phosphoric acid as promoter affording quantitative conversion with 92% selectivity towards decene oxide. Unfortunately, the addition of CO2 from the start (auto-tandem catalysis) gave low yields of decene carbonate (10%). On the contrary, the addition of 1 atm CO2 and tetrabutyl ammonium iodide after completion of the epoxidation first step without any intermediate work-up (assisted-tandem catalysis) afforded a 94% yield in decene carbonate. The protocol could be scaled up to a 10 gram scale. The scope of the reaction was demonstrated for primary aliphatic olefins with different alkyl chain lengths (C6-C16), while cyclic and aromatic activated olefins such as cyclohexene and styrene suffered from the formation of undesired overoxidation products in the first step.
Metalated-bipyridine-based porous hybrid polymers with POSS-derived Si-OH groups for synergistic catalytic CO2fixation
Zhang, Yadong,Luo, Niu,Xu, Jingyu,Liu, Ke,Zhang, Shengqi,Xu, Qinglin,Huang, Rui,Long, Zhouyang,Tong, Minman,Chen, Guojian
, p. 11300 - 11309 (2020/09/02)
Herein, we construct a new series of N-heterocyclic ligand bipyridine-based porous hybrid polymers (denoted Bpy-PHPs) from the Heck reaction of a rigid building unit octavinylsilsesquioxane (VPOSS) and 5,5′-dibromo-2,2′-bipyridine. Surprisingly, the typical sample Bpy-PHP-4 was found to be a metal-/halogen-free heterogeneous catalyst in the cycloaddition reaction of CO2 with a few epoxides under atmospheric pressure. After coordination with ZnBr2, the resultant ZnBr2@Bpy-PHP-4 afforded largely enhanced heterogeneous catalytic activities upon the conversion of carbon dioxide (CO2) and various epoxides into cyclic carbonates without using any co-catalysts under mild conditions. The moderate catalytic activities of Bpy-PHP-4 may be due to the presence of hydrogen bond donors (HBDs), i.e., polyhedral oligomeric silsesquioxane (POSS)-derived Si-OH groups and N active sites from Bpy linkers. In comparison, the high catalytic efficiency of ZnBr2@Bpy-PHP-4 should be attributed to the synergistic catalysis of Si-OH groups, N active atoms, and Bpy-coordinated ZnBr2. Moreover, the catalyst ZnBr2@Bpy-PHP-4 can be easily recovered and reused ten times without any significant loss of catalytic activities. This work affords an efficient metal-based porous hybrid polymer heterogeneous catalyst for the cycloaddition reaction of CO2 and epoxides under mild and co-catalyst-free conditions.
Selective Conversion of CO 2 and Switchable Alcohols into Linear or Cyclic Carbonates via Versatile Zinc Catalysis
Song, Qing-Wen,Zhao, Qing-Ning,Li, Jing-Yuan,Zhang, Kan,Liu, Ping
, p. 739 - 746 (2019/01/23)
It is promising and challenging to achieve the effective construction of carbonates using CO 2 and a non-noble metal catalyst. Herein, selective catalytic conversion of CO 2 and switchable alcohol candidates to produce linear or cyclic carbonates and α-hydroxy ketones via effective zinc catalyst was developed. A series of primary alcohols and cyclohexanol, 1,2-diols, and water can serve as nucleophiles to give alkyl or aryl 2-substituted-3-oxobutan-2-yl carbonates, substituted 1,3-dioxolan-2-ones, 3-substituted 3-hydroxybutan-2-ones, respectively with excellent selectivity and high yields.
Methoxy Groups Increase Reactivity of Bifunctional Tetraarylphosphonium Salt Catalysts for Carbon Dioxide Fixation: A Mechanistic Study
Toda, Yasunori,Komiyama, Yutaka,Esaki, Hiroyoshi,Fukushima, Kazuaki,Suga, Hiroyuki
supporting information, p. 15578 - 15589 (2019/11/21)
The development of carbon dioxide fixation under mild conditions is a central theme in organic synthesis. Despite the tremendous progress in the field of organocatalysis in the past two decades, the coupling reactions of epoxides with carbon dioxide that proceed at atmospheric pressure at temperatures of less than 100 °C have remained challenging. In our aspirational studies of tetraarylphosphonium salts (TAPS) catalysis, we report here the bifunctional TAPS-catalyzed synthesis of five-membered cyclic carbonates by chemical fixation using 1 atm of carbon dioxide at 60 °C. Intriguing substituent effects of TAPS were observed, in which electron-donating groups enhanced their reactivity. In addition, the mechanism was thoroughly investigated by undertaking both experimental and theoretical studies, suggesting that the electronic properties of TAPS affect carbon dioxide insertion into halohydrin intermediates. The results provided fruitful information to understand the origin of the TAPS behavior, which would contribute to the design of novel catalysts for carbon dioxide capture.
Post-modified porphyrin imine gels with improved chemical stability and efficient heterogeneous activity in CO2 transformation
Liao, Peisen,Cai, Guangmei,Shi, Jianying,Zhang, Jianyong
, p. 10017 - 10024 (2019/07/04)
Efficient heterogeneous gel catalysts have been developed based on dynamic covalent chemistry and post-modification methods for the chemical fixation of CO2. Various porphyrin-based imine gels are synthesized and subsequent reduction of imine bonds and metallation with various metal centers yields gel catalysts. The gels are characterized by a number of techniques including SEM, TEM, EDX, FT-IR, CP/MAS 13C NMR, and XPS. The resulting gels not only have network structures including micro-, meso- and macropores, but also show improved chemical stability and strong interactions between CO2 and pore channels. The gel catalysts show good catalytic activity towards the cycloaddition of epoxides with CO2 to cyclic carbonates using wet gels. Post-modified gel catalysts with a Zn(ii) center (ZnTAPP-Go-r) show a high product yield and high stability with recyclability over 5 cycles.
Straightforward synthesis of MTW-type magnesium silicalite for CO2 fixation with epoxides under mild conditions
Wen, Haimeng,Xie, Jingyan,Zhou, Yang,Zhou, Yu,Wang, Jun
, p. 5725 - 5735 (2019/10/23)
Aluminum-free magnesium silicalite with MTW topology (Mg-Si-ZSM-12) was fabricated via a straightforward hydrothermal synthesis route involving an initial acid co-hydrolysis step. Mg incorporation endowed superior basic properties to the MTW framework, as illustrated by CO2 sorption and temperature programmed desorption plus the activity in a typical basic reaction, Knoevenagel condensation. Mg-Si-ZSM-12 catalyzed the coupling of atmospheric CO2 with epoxides and led to the efficient production of cyclic carbonates with high yield and selectivity at relatively low temperature (down to 60 °C). The present strategy afforded a zeolitic solid base with regular 12-membered ring microporous channels that has potential application in CO2 fixation.
Method for chemically fixing carbon dioxide to synthesize cyclic carbonate under normal temperature and normal pressure condition of eutectic ionic liquid (by machine translation)
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Paragraph 0030; 0039; 0041, (2019/07/16)
The method uses carbon dioxide and different substituent epoxy compounds as raw materials, adopts quaternary phosphonium bromide salt, aminophenol according to molar ratio ?timetime?: 3, the reaction pressure of 5%~10% and the reaction temperature of 12~24 unitunitz ?, and the 1:2~1 reaction time ranges hours to synthesize the corresponding cyclic carbonate . the method comprises the following steps: preparing a catalyst, and synthesizing 0.1 mpa the cyclic carbonate by 25 °C using the novel eutectic ionic liquid in a molar ratio of carbon dioxide and different substituted base epoxy compounds. The novel eutectic ionic liquid is simple and efficient in preparation, cheap and accessible in raw materials, excellent in catalytic performance, and capable of realizing high-selectivity synthesis of cyclic carbonate under normal temperature, normal pressure and the like. , The invention avoids the use, the catalyst and the product of the toxic transition metal, the volatile organic solvent and the cocatalyst, and belongs to an environment-friendly catalyst. (by machine translation)
