135682-18-7Relevant articles and documents
Hollow and microporous catalysts bearing Cr(III)-F porphyrins for room temperature CO2 fixation to cyclic carbonates
Kim, Myung Hyun,Song, Taemoon,Seo, Ue Ryung,Park, Ji Eun,Cho, Kyoungil,Lee, Sang Moon,Kim, Hae Jin,Ko, Yoon-Joo,Chung, Young Keun,Son, Seung Uk
, p. 23612 - 23619 (2017)
Hollow and microporous metal free/Cr-porphyrin networks were prepared via the Sonogashira coupling of metal-free or Cr-tetra(4-ethynylphenyl) porphyrins and 1,4-diiodobenzene on the surface of silica templates followed by silica etching. Zinc was introduced into a hollow and microporous metal free porphyrin network (H-MPN) through post-synthetic modification to form a H-MZnPN. Hollow and microporous Cr(iii)-F porphyrin networks (H-MCrPNs) showed the best catalytic activities in room temperature CO2 fixation with epoxides to cyclic carbonates. In addition, the H-MCrPN could be reused at least for five runs, maintaining the original catalytic activity. The good performance of the H-MCrPN is attributed to its microporosity, the shortened diffusion pathways for substrates due to the hollow structure, and the efficient Lewis acidic activity of Cr(iii)-F moieties.
Poly(hydroxyurethane): Catalytic applicability for the cyclic carbonate synthesis from epoxides and CO2
Motokucho, Suguru,Morikawa, Hiroshi
, p. 10678 - 10681 (2020)
We have developed a synthetic methodology using poly(hydroxyurethane) as an organocatalyst for the chemical fixation of CO2 into epoxides, leading to the formation of five-membered cyclic carbonates with remarkably high selectivity and yields. The catalyzed reaction was applicable to various epoxides.
Novel hydrazine-bridged covalent triazine polymer for CO2 capture and catalytic conversion
Liu, Anhua,Zhang, Jinju,Lv, Xiaobing
, p. 1320 - 1328 (2018)
Carbon dioxide (CO2) capture and catalytic conversion has become an attractive and challenging strategy for CO2 utilization since it is an abundant, inexpensive, and renewable C1 resource and a main greenhouse gas. Herein, a novel hydrazine-bridged covalent triazine polymer (HB-CTP) was first designed and synthesized through simple polymerization of cyanuric chloride with 2,4,6-trihydrazinyl-1,3,5-triazine. The resultant HB-CTP exhibited good CO2 capture capacity (8.2 wt%, 0 °C, and 0.1 MPa) as well as satisfactory recyclability after five consecutive adsorption-desorption cycles. Such a polymer was subsequently employed as a metal-free heterogeneous catalyst for the cyclo-addition of CO2 with various epoxides under mild and solvent-free conditions, affording cyclic carbonates with good to excellent yields (67%–99%) and high functional-group tolerance. The incorporation of hydrazine linkages into HB-CTP's architecture was suggested to play the key role in activating epoxides through hydrogen bonding. Moreover, HB-CTP can be reused at least five times without significant loss of its catalytic activity.
Zinc–Azatrane Complexes as Efficient Catalysts for the Conversion of Carbon Dioxide into Cyclic Carbonates
Bousquet, Benjamin,Martinez, Alexandre,Dufaud, Véronique
, p. 843 - 848 (2018)
Three Zn complexes based on the N4-tris(2-aminoethyl)amine (tren) chelating ligand and presenting a C3-symmetrical axis were synthesized and successfully applied in the coupling of CO2 with terminal and internal epoxides. These complexes proved to be efficient catalysts if associated with tetrabutylammonium iodide, even at a low catalyst loading (0.005 mol %) or at room temperature, and allowed the production of cyclic carbonates in good to high yields. Variation of the substitution pattern on the tren ligand was shown to impact the catalyst performance greatly, and the highest turnover number (TON) (up to 11 200) was achieved with the less sterically hindered methyl-substituted ZnII–azatrane complex. These binary Zn–azatrane/NBu4I catalytic systems could be applied to a wide range of epoxide substrates, including the more challenging internal epoxides. Moreover, although soluble in the reaction medium, Zn–azatrane catalysts could be easily recovered and reused up to three times without any substantial loss in activity, proving their robustness under the reaction conditions.
Benzotriazolium ionic liquid immobilized on periodic mesoporous organosilica as an effective reusable catalyst for chemical fixation of CO2into cyclic carbonates
Hu, Yu Lin,Li, Jing Rui
, (2020)
A type of dichloro(dimethoxyethane)nickel anionic benzotriazolium ionic liquid-functionalized periodic mesoporous organosilicas were synthesized and tested as effective and practical heterogeneous catalysts in the cycloaddition of CO2 with epoxides. The catalyst PMO?ILC4H10O2NiCl3(1.0) showed brilliant catalytic activity for the synthesis of cyclic carbonates with high yields and selectivities under solvent- and cocatalyst-free conditions. We also found that the catalytic activity could be significantly influenced by the hydroxyl groups sites of periodic mesoporous organosilica and the active sites (hydroxyl groups/ dichloro(dimethoxyethane)nickel anion) of the benzotriazoliumcation ionic liquid, probably due to an intensification of intramolecular synergistic effect. The catalytic process displayed ease of recovery, excellent stability and recyclability for at least five runs without significant loss of its catalytic activity.
Cycloaddition of carbon dioxide and epoxides catalyzed by rare earth metal complexes bearing a Trost ligand
Cheng, Jun,Lu, Chengrong,Zhao, Bei
, p. 13096 - 13103 (2021)
A series of rare earth metal complexes (Sm (1), Eu (2), Y (3), Yb (4), and Lu (5)) based on Trost ligands were synthesized and well characterized, and catalyzed the cycloaddition of carbon dioxide and epoxides successfully. The combination of 1 mol% Sm-based complex1with 2 mol% tetrabutylammonium bromide (TBAB) was proved to be the optimal catalyst system for the formation of the monosubstituted cyclic carbonate at 70 °C under the atmospheric pressure. While for the more challenging disubstituted epoxides, the adduct cyclic carbonates were successfully obtained when the pressure of CO2was elevated to 0.7 MPa.
Glycerol carboxylation to glycerol carbonate in the presence of rhodium complexes with nitrogen-containing macroligands
Ezhova,Korosteleva,Kolesnichenko,Kuz'Min,Khadzhiev,Sorokina,Vasil'Eva,Voronina
, p. 416 - 421 (2012)
The carboxylation of glycerol to glycerol carbonate (GC) in the presence of rhodium complexes with N-containing macroligands (polyethyleneimine and chitosan) has been studied. It has been found that the {RhCl3 + chitosan} system is an effective catalyst. It is most effective in the presence of methyl iodide or in the case of introduction of carbonates (dimethyl carbonate, propylene carbonate) into the reaction zone. The carboxylation of glycerol occurs at temperatures of 140-180°C in a methanol solution in a reducing environment under a pressure of 50 atm (40 atm of CO and 10 atm of H2). The turnover number of the rhodium catalyst for the reaction time is 10 to 120. Pleiades Publishing, Ltd., 2012.
Facile synthesis of a dimeric titanium(iv) complex with terminal TiO moieties and its application as a catalyst for the cycloaddition reaction of CO2 to epoxides
Kim, Hyejin,Choi, Sung Ho,Ahn, Duseong,Kim, Yoseph,Ryu, Ji Yeon,Lee, Junseong,Kim, Youngjo
, p. 97800 - 97807 (2016)
In this report, facile and exclusive synthesis of dimeric titanium(iv) complex with a terminal TiO moiety from the reaction between novel pyridine-based tridentate ligand (LH2) and Ti(O-i-Pr)4 under the bubbling of wet air is presented. Alternatively, the same dimeric Ti complex was obtained via wet air bubbling of monomeric LTi(O-i-Pr)2 or addition of the same equiv. of H2O into LTi(O-i-Pr)2. All compounds including LH2 and two titanium complexes were characterized by single crystal X-ray analyses. Newly synthesized terminal oxo-titanium compound is the first example of structurally characterized dimeric terminal oxo-titanium compound having no TiO→Ti bonds. Two titanium complexes were used as effective catalysts for the cycloaddition of CO2 to propylene oxide in the presence of various kinds of cocatalysts such as n-Bu4PBr, n-Bu4NI, n-Bu4NBr, n-Bu4NCl, PPNCl, and DMAP.
Cycloaddition of CO2 to epoxides over both homogeneous and silica-supported guanidine catalysts
Barbarini, Alessandro,Maggi, Raimondo,Mazzacani, Alessandro,Mori, Giovanni,Sartori, Giovanni,Sartorio, Raffaella
, p. 2931 - 2934 (2003)
The synthesis of cyclic carbonates by CO2 insertion into epoxides catalysed by both homogeneous MTBD and TDB supported on MCM-41 mesoporous silica is reported.
Lewis acid-base bifunctional aluminum-salen catalysts: synthesis of cyclic carbonates from carbon dioxide and epoxides
Ren, Yanwei,Jiang, Ou,Zeng, Hang,Mao, Qiuping,Jiang, Huanfeng
, p. 3243 - 3249 (2016)
Two Lewis acid-base bifunctional monometallic aluminum-salen complexes were prepared based on a new type of salen ligand with two N-methylhomopiperazine moieties at the 3,3′-position. The Al(salen) complexes proved to be efficient and recyclable homogeneous catalysts towards the organic solvent-free synthesis of cyclic carbonates from epoxides and CO2 in the absence of a co-catalyst, in which >90% yield of cyclic carbonate could be obtained under relatively mild conditions. The catalysts can be easily recovered and reused five times without significant loss of activity and selectivity. Furthermore, the Lewis acid-base cooperative activation mechanism by the bifunctional Al(salen) complexes was proposed according to experimental data.
Scorpionate Catalysts for Coupling CO2 and Epoxides to Cyclic Carbonates: A Rational Design Approach for Organocatalysts
Hong, Mannkyu,Kim, Yoseph,Kim, Hyejin,Cho, Hee Jin,Baik, Mu-Hyun,Kim, Youngjo
, p. 9370 - 9380 (2018)
Novel scorpionate-type organocatalysts capable of effectively coupling carbon dioxide and epoxides under mild conditions to afford cyclic propylene carbonates were developed. On the basis of a combined experimental and computational study, a precise mechanistic proposal was developed and rational optimization strategies were identified. The epoxide ring-opening, which requires an iodide as a nucleophile, was enhanced by utilizing an immonium functionality that can form an ion pair with iodide, making the ring-opening process intramolecular. The CO2 activation and cyclic carbonate formation were catalyzed by the concerted action of two hydrogen bonds originating from two phenolic groups placed at the claw positions of the scorpionate scaffold. Electronic tuning of the hydrogen bond donors allowed to identify a new catalyst that can deliver >90% yield for a variety of epoxide substrates within 7 h at room temperature under a CO2 pressure of only 10 bar, and is highly recyclable.
Conversion of dilute CO2to cyclic carbonates at sub-atmospheric pressures by a simple indium catalyst
Baalbaki, Hassan A.,Roshandel, Hootan,Hein, Jason E.,Mehrkhodavandi, Parisa
, p. 2119 - 2129 (2021)
The transformation of CO2to value added commodity chemicals presents an impactful strategy to obtain products that are less dependent on fossil fuels. In this study, indium tribromide (InBr3) mixed with tetrabutylammonium bromide (NBu4Br) co-catalyst has been identified as a simple, highly efficient catalyst for the synthesis of cyclic carbonates from epoxides and CO2at sub-atmospheric pressures, room temperature, and under solvent-free conditions. The InBr3/NBu4Br catalytic system is tolerant toward different functional groups with high conversions and >99% selectivity for cyclic carbonate without resorting to high pressures and temperatures. Moreover, a combination ofin situIR, NMR spectroscopy, and substrate labelling experiments enabled the proof of key catalytic steps and detection of reaction intermediates to elucidate the reaction mechanism. This technology represents a potential scalable system for the utilization of waste CO2
Synthesis of Homo- And Heteronuclear Rare-Earth Metal Complexes Stabilized by Ethanolamine-Bridged Bis(phenolato) Ligands and Their Application in Catalyzing Reactions of CO2 and Epoxides
Hua, Linyan,Li, Baoxia,Han, Cuiting,Gao, Pengfei,Wang, Yaorong,Yuan, Dan,Yao, Yingming
, p. 8775 - 8786 (2019)
A series of homonuclear rare-earth (RE) metal complexes (1Y, 2Yb, 3Nd, and 4La) and heteronuclear RE-Zn complexes (1Y-Zn, 3Nd-Zn, and 5Sm-Zn) stabilized by ethanolamine-bridged bis(phenolato) ligands was prepared and structurally characterized. Heteronuclear complexes are assembled through bridging acetate ligands, and their formation and characterization add to the diversity of 3d-4f complexes. Their activities in mediating reactions of CO2 and epoxides were evaluated and compared. Heteronuclear RE-Zn complexes found application in the copolymerization of cyclohexene oxide and CO2, giving rise to acetate-group-capped copolymers. Homonuclear complexes showed good activity in catalyzing the cycloaddition of variously monosubstituted epoxides and CO2 (1 bar), generating cyclic carbonates in 65-96% yield. For sterically hindered disubstituted epoxides, good yields of 60-91% were achieved in the presence of 10 bar CO2
Carbonate Formation from Oxiranes and Carbon Dioxide Catalyzed by Organotin Halide-Tetraalkylphosphonium Halide Complexes
Baba, Akio,Nozaki, Takashi,Matsuda, Haruo
, p. 1552 - 1554 (1987)
Cycloaddition of carbon dioxide to oxiranes was excellently promoted by the complexes of organotin halides and tetraalkylonium halides, while either components of the complexes had no catalytic activity individually.Particularly, the complex composed of Bu3SnI-Bu4PI was the most favorable catalyst, yielding a variety of fivemembered cyclic carbonates under neutral and mild conditions.
Plasma-Assisted Immobilization of a Phosphonium Salt and Its Use as a Catalyst in the Valorization of CO2
Brüser, Volker,Epping, Jan Dirk,Frank, Marcus,Hu, Yuya,Longwitz, Lars,Peglow, Sandra,Werner, Thomas
, (2020)
The first plasma-assisted immobilization of an organocatalyst, namely a bifunctional phosphonium salt in an amorphous hydrogenated carbon coating, is reported. This method makes the requirement for prefunctionalized supports redundant. The immobilized catalyst was characterized by solid-state 13C and 31P NMR spectroscopy, SEM, and energy-dispersive X-ray spectroscopy. The immobilized catalyst (1 mol %) was employed in the synthesis of cyclic carbonates from epoxides and CO2. Notably, the efficiency of the plasma-treated catalyst on SiO2 was higher than those of the SiO2 support impregnated with the catalyst and even the homogeneous counterpart. After optimization of the reaction conditions, 13 terminal and four internal epoxides were converted with CO2 to the respective cyclic carbonates in yields of up to 99 %. Furthermore, the possibility to recycle the immobilized catalyst was evaluated. Even though the catalyst could be reused, the yields gradually decreased from the third run. However, this is the first example of the recycling of a plasma-immobilized catalyst, which opens new possibilities in the recovery and reuse of catalysts.
Continuous-Flow O-Alkylation of Biobased Derivatives with Dialkyl Carbonates in the Presence of Magnesium–Aluminium Hydrotalcites as Catalyst Precursors
Cattelan, Lisa,Perosa, Alvise,Riello, Piero,Maschmeyer, Thomas,Selva, Maurizio
, p. 1571 - 1583 (2017)
The base-catalysed reactions of OH-bearing biobased derivatives (BBDs) including glycerol formal, solketal, glycerol carbonate, furfuryl alcohol and tetrahydrofurfuryl alcohol with non-toxic dialkyl carbonates (dimethyl and diethyl carbonate) were explored under continuous-flow (CF) conditions in the presence of three Na-exchanged Y- and X-faujasites (FAUs) and four Mg–Al hydrotalcites (HTs). Compared to previous etherification protocols mediated by dialkyl carbonates, the reported procedure offers substantial improvements not only in terms of (chemo)selectivity but also for the recyclability of the catalysts, workup, ease of product purification and, importantly, process intensification. Characterisation studies proved that both HT30 and KW2000 hydrotalcites acted as catalyst precursors: during the thermal activation pre-treatments, the typical lamellar structure of the hydrotalcite was broken down gradually into a MgO-like phase (periclase) or rather a magnesia–alumina solid solution, which was the genuine catalytic phase.
Catalytic, Kinetic, and Mechanistic Insights into the Fixation of CO2 with Epoxides Catalyzed by Phenol-Functionalized Phosphonium Salts
Hu, Yuya,Wei, Zhihong,Frey, Anna,Kubis, Christoph,Ren, Chang-Yue,Spannenberg, Anke,Jiao, Haijun,Werner, Thomas
, p. 363 - 372 (2020/11/30)
A series of hydroxy-functionalized phosphonium salts were studied as bifunctional catalysts for the conversion of CO2 with epoxides under mild and solvent-free conditions. The reaction in the presence of a phenol-based phosphonium iodide proceeded via a first order rection kinetic with respect to the substrate. Notably, in contrast to the aliphatic analogue, the phenol-based catalyst showed no product inhibition. The temperature dependence of the reaction rate was investigated, and the activation energy for the model reaction was determined from an Arrhenius-plot (Ea=39.6 kJ mol?1). The substrate scope was also evaluated. Under the optimized reaction conditions, 20 terminal epoxides were converted at room temperature to the corresponding cyclic carbonates, which were isolated in yields up to 99 %. The reaction is easily scalable and was performed on a scale up to 50 g substrate. Moreover, this method was applied in the synthesis of the antitussive agent dropropizine starting from epichlorohydrin and phenylpiperazine. Furthermore, DFT calculations were performed to rationalize the mechanism and the high efficiency of the phenol-based phosphonium iodide catalyst. The calculation confirmed the activation of the epoxide via hydrogen bonding for the iodide salt, which facilitates the ring-opening step. Notably, the effective Gibbs energy barrier regarding this step is 97 kJ mol?1 for the bromide and 72 kJ mol?1 for the iodide salt, which explains the difference in activity.
The catalytic system ‘Rhodamine B/additive’ for the chemical fixation of CO2
Wu, Feng-tian,Wu, Ling,Cui, Chun-na
, (2021/02/09)
The catalytic system ‘Rhodamine B/additive’ was introduced to promote the CO2 reactions. We synthesized various cyclic carbonates in good to excellent yields under the catalysis of rhodamine B and TBAB. A variety of 2-oxazolidinone derivatives were obtained in the presence of rhodamine B and DBU.
