96-49-1Relevant articles and documents
Synthesis of Cyclic Carbonates from Carbon Dioxide and Epoxides in the Presence of Organoantimony Compounds as Novel Catalysts
Nomura, Ryoki,Ninagawa, Akira,Matsuda, Haruo
, p. 3735 - 3738 (1980)
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.
Comprehensive insight into the support effect of graphitic carbon nitride for zinc halides on the catalytic transformation of CO2 into cyclic carbonates
Xu, Jie,Gan, Yu-Lin,Hu, Peng,Zheng, Huan,Xue, Bing
, p. 5582 - 5593 (2018)
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%).
Microporous Polymeric Spheres as Highly Efficient and Metal-Free Catalyst for the Cycloaddition of CO2 to Cyclic Organic Carbonates at Ambient Conditions
Ding, Shunmin,Sun, Ling,Ma, Xiaohua,Cheng, Dan,Wu, Shaohua,Zeng, Rong,Deng, Shengjun,Chen, Chao,Zhang, Ning
, p. 2970 - 2977 (2020)
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.].
Homogenous dual-ligand zinc complex catalysts for chemical fixation of CO2 to propylene carbonate
Shi, Yan-Li,Zhang, Peng,Liu, Ding-Hua,Zhou, Peng-Fei,Sun, Lin-Bing
, p. 1673 - 1682 (2015)
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
A simple synthesis of ethylene carbonate from carbon dioxide and 2-chloroethanol using silica gel as a catalyst
Lyubimov, Sergey E.,Zvinchuk, Anastasia A.,Sokolovskaya, Marina V.,Davankov, Vadim A.,Chowdhury, Biswajit,Zhemchugov, Pavel V.,Arzumanyan, Ashot V.
, (2020)
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.
New mechanistic insight into the coupling reactions of CO2 and epoxides in the presence of zinc complexes
Kim, Hoon Sik,Kim, Jai Jun,Lee, Sang Deuk,Lah, Myoung Soo,Moon, Dohyun,Jang, Ho Gyeom
, p. 678 - 686 (2003)
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.
Imidazolium ionic liquids/organic bases: Efficient intermolecular synergistic catalysts for the cycloaddition of CO2 and epoxides under atmospheric pressure
Ji, Liangzheng,Luo, Zhoujie,Zhang, Yongya,Wang, Rong,Ji, Yayan,Xia, Fei,Gao, Guohua
, p. 124 - 130 (2018)
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.
Realizing metal-free carbene-catalyzed carbonylation reactions with CO
Peltier, Jesse L.,Eder Tomás-Mendivil,Tolentino, Daniel R.,Hansmann, Max M.,Jazzar, Rodolphe,Bertrand, Guy
, p. 18336 - 18340 (2020)
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.
Stereochemistry of copper- and nickel-catalyzed insertion of carbon dioxide into epoxides. A microwave study
Baeckvall, Jan-E.,Karlsson, Ola,Ljunggren, Stig O.
, p. 4985 - 4988 (1980)
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.
Formation of Cyclic Carbonates from CO2 and Epoxides Catalyzed by a Cobalt-Coordinated Conjugated Microporous Polymer
Xiong, Jian,Yang, Rui-Xia,Xie, Yong,Huang, Nian-Yu,Zou, Kun,Deng, Wei-Qiao
, p. 2584 - 2587 (2017)
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.
