13818-44-5Relevant articles and documents
Synthesis of cyclic carbonates from carbon dioxide and epoxides catalyzed by a keggin-type polyoxometalate-supported rhenium carbonyl derivate in ionic liquid
Huo, Zhiyuan,Zhao, Juan,Bu, Zhanwei,Ma, Pengtao,Liu, Qisen,Niu, Jingyang,Wang, Jingping
, p. 3096 - 3100 (2014)
A monovacant Keggin-type polyoxometalate-supported trirhenium carbonyl derivate [(CH3)4N]5H23[(PW11O39){Re(CO)3}3(μ3-O)(μ2-OH)]4·24H2O was synthesized. It was used as a catalyst for the synthesis of cyclic carbonates from carbon dioxide and epoxides under mild reaction conditions with co-catalyst pyrrolidinium bromide. The catalyst system was recycled 10 times with only a small decline in yield. The catalytic mechanism was hypothesized based on experimental results and the frontier orbitals computed by DFT calculations.
New iron pyridylamino-bis(Phenolate) catalyst for converting CO2 into cyclic carbonates and cross-linked polycarbonates
Taherimehr, Masoumeh,Sert?, Jo?o Paulo Cardoso Costa,Kleij, Arjan W.,Whiteoak, Christopher J.,Pescarmona, Paolo P.
, p. 1034 - 1042 (2015)
The atom-efficient reaction of CO2 with a variety of epoxides has been efficiently achieved employing iron pyridylamino-bis(phenolate) complexes as bifunctional catalysts. The addition of a Lewis base co-catalyst allowed significant reduction in the amount of iron complex needed to achieve high epoxide conversions. The possibility of controlling the selectivity of the reaction towards either cyclic carbonate or polycarbonate was evaluated. An efficient switch in selectivity could be achieved when cyclic epoxides such as cyclohexene oxide and the seldom explored 1,2-epoxy-4-vinylcyclohexane were used as substrates. The obtained poly(vinylcyclohexene carbonate) presents pending vinyl groups, which allowed post-synthetic cross-linking by reaction with 1,3-propanedithiol. The cross-linked polycarbonate displayed a substantial increase in the glass transition temperature and chemical resistance, thus opening new opportunities for the application of these green polymers. CO2 meets epoxides: Iron pyridylamino-bis(phenolate) complexes are highly active catalysts for the atom-efficient reaction of CO2 with a variety of epoxides. The selectivity can be switched between the cyclic or polymeric carbonate when using cyclic epoxides such as cyclohexene oxide and 1,2-epoxy-4-vinylcyclohexaneas substrates. Cross-linking of the obtained poly(vinylcyclohexene carbonate) leads to substantial increase in the Tg and chemical resistance of the polymer.
Bifunctional one-component catalysts for the addition of carbon dioxide to epoxides
Büttner, Hendrik,Lau, Kornelia,Spannenberg, Anke,Werner, Thomas
, p. 459 - 467 (2015)
Several bifunctional ammonium salts were synthesized and employed as one-component catalysts for the conversion of CO2 and epoxides to produce cyclic carbonates. These catalysts show superior activities compared to their monofunctional analogs. A turnover number of up to 693 and a turnover frequency of up 392h-1 could be achieved for the best catalyst. Moreover, the effect of various solvents has been studied. All employed solvents and the product formed had a negative influence on substrate conversion. The scope and limitation of the reaction has been studied carefully for two general reaction protocols at 45 and 90-°C. In over 20 examples, the isolated yields after filtration were 90-%. In addition, we present the first organocatalyzed synthesis of a cyclohexene-based naturally occurring cyclic carbonate, and its molecular structure was determined by XRD. Furthermore, we demonstrate that the reaction can be performed even on a multigram scale and can be monitored by insitu FTIR spectroscopy. Couple up: Recyclable bifunctional ammonium salts are identified as one-component catalysts for the 100-% atom-economic coupling reaction of CO2 and epoxides even at 45-°C. The alcohol moiety that donates a hydrogen bond accelerates the catalytic reaction remarkably. This metal and solvent-free process can be performed on a multigram scale and is applied to the synthesis of a naturally occurring cyclic carbonate.
Transparent, flexible and highly conductive ion gels from ionic liquid compatible cyclic carbonate network
Jana, Satyasankar,Parthiban, Anbanandam,Chai, Christina L. L.
, p. 1488 - 1490 (2010)
Transparent, flexible, self-standing and highly ion conductive ion gels have been synthesised from novel ionic liquid compatible cyclic carbonate (CC) network polymer. The use of dual functional cyclic carbonate methacrylate (CCMA) monomer for the synthes
Synthesis of bifunctional cyclic carbonates from CO2 catalysed by choline-based systems
Amaral, Adérito J.R.,Coelho, Jorge F.J.,Serra, Arménio C.
, p. 5518 - 5522 (2013)
Easily prepared choline iodide is an active catalyst for the synthesis of cyclic carbonates through the coupling reaction of CO2 and epoxides using low pressure (1 MPa), moderate temperature (85 °C) and green solvents (ethanol and propan-2-ol). The effects of reaction temperature, pressure, reaction time and amount of catalyst used were also investigated. The results showed moderate to high yields and excellent selectivities of cyclic carbonates with vinyl or acrylate groups under mild reaction conditions. The heterogenization of choline over a Merrifield resin gives access to a supported catalyst with good recyclability and reactivity that can be extended to a variety of terminal epoxide substrates.
Facile CO2 Cycloaddition to Epoxides by Using a Tetracarbonyl Metal Selenotungstate Derivate [{Mn(CO)3}4(Se2W11O43)]8-
Lu, Jingkun,Ma, Xinyi,Singh, Vikram,Zhang, Yujiao,Wang, Ping,Feng, Junwei,Ma, Pengtao,Niu, Jingyang,Wang, Jingping
, p. 14632 - 14643 (2018)
A novel polyoxometalate cluster, i.e., Na1.5H4.5[(CH3)4N]2{[Mn(CO)3]4(Se2W11O43)}·9H2O (1), has been successfully synthesized under moderately acidic conditions. Compound 1 contains four electron-donating {Mn(CO)3}+ organometallic entities, which are grafted over an unprecedented heteropolytungstate electron-acceptor group. Compound 1 was further structurally characterized by various physicochemical techniques like elemental analyses, inductively coupled plasma (ICP) analyses, IR and UV-vis spectroscopy, electrochemistry, and single-crystal X-ray diffraction, and so on. The polyoxoanion of 1 comprises a novel {Se2W11} fragment, which is obtained from molecular assembly of rare {SeW3} and {SeW8} species. Evaluation of the data from solution-state IR spectrum showed excellent agreement with the solid state IR spectrum, indicating the intact clusters in the CH3CN/Na2SO4 solvent. Also, negative electrospray ionization mass spectrometry (ESI-MS) was an alternative tool to verify the stability of 1 in the mixed solvent. Additionally, the resulting hybrid can act as a catalyst for cyclic carbonate formation from the reactants epoxides and CO2 under modest reaction conditions in conjunction with a 1-ethyl-1-methylpyrrolidinium bromide (2). The good activity can be substantiated due to the cooperative influence of polyoxoanion and Br- ions. Complex 1 can also be easily recycled and reused three times without obvious decrease of catalytic activity.
Multifunctional and Sustainable Fe-Iminopyridine Complexes for the Synthesis of Cyclic Carbonates
Seong, Eun Young,Kim, Jae Hyung,Kim, Nam Hee,Ahn, Kwang-Hyun,Kang, Eun Joo
, p. 409 - 415 (2019)
The use of multifunctional and sustainable Fe catalysts for the formation of cyclic carbonates from epoxides and carbon dioxide at 80 °C and 3 bar pressure is presented. The optimal catalyst possesses a halide counteranion and a hydrogen bond donor to activate the epoxide for ring opening, affording a single-component, cocatalyst-free catalytic system.
High conversion of CO2 into cyclic carbonates under solvent free and ambient pressure conditions by a Fe-cyanide complex
Jiang, Pengbo,Ma, Lei,Wang, Kaizhi,Lan, Kai,Zhan, Zhenzhen,Iqbal, Anam,Niu, Fang,Li, Rong
, p. 17211 - 17219 (2019)
Methods of converting carbon dioxide into valuable chemicals are of great demand but their development is still challenging. Herein, we developed an efficient, green and facile synthetic method for the preparation of a Fe-cyanide complex. The target catalyst showed high catalytic activity for the cyclic reaction of carbon dioxide and epoxide under solvent free conditions and ambient pressure. Meanwhile, the effects of morphology of different catalysts on their catalytic activities were also investigated by the kinetic and thermodynamic studies. In addition, the catalyst could be recycled and reused for at least five successive cycles without significant decrease in the catalytic activity. This target catalyst thus represents one of the efficient and recyclable systems reported for the cyclic reaction in industry.
Pseudopeptidic macrocycles as cooperative minimalistic synzyme systems for the remarkable activation and conversion of CO2in the presence of the chloride anion
Altava, Belén,Bolte, Michael,Burguete, M. Isabel,Esteve, Ferran,García-Verdugo, Eduardo,Luis, Santiago V.
, p. 4697 - 4705 (2020)
A series of pseudopeptidic compounds have been assayed as organocatalyts for the conversion of CO2 into organic carbonates through a cooperative multifunctional mechanism. Conformationally constrained pseudopeptidic macrocycles 3a and 3b have been revealed to be excellent synzymes for this purpose, being able to provide a suitable preorganization of the different functional elements and reaction components to activate the CO2 molecule and stabilize the different anionic intermediates involved, through a series of cooperative supramolecular interactions. As a result, remarkable catalytic efficiencies are found at low CO2 pressures and moderate temperatures, with TON and TOF values surpassing those reported for other organocatalytic supramolecular systems under similar conditions. The process works well for monosubstituted epoxides. The involvement of the different structural elements has been analyzed in detail and preliminary studies show the potential for recovery and reuse of these catalytic systems.
Polyvinyl alcohol-potassium iodide: An efficient binary catalyst for cycloaddition of epoxides with CO2
Chang, Haibo,Li, Qingshuo,Cui, Xuemin,Wang, Hongxia,Qiao, Congzhen,Bu, Zhanwei,Lin, Tong
, p. 25 - 30 (2018)
In this study, we have for the first time demonstrated that polyvinyl alcohol (PVA) and potassium iodide (KI) can form an efficient catalytic system for synthesis of cyclic carbonates from epoxide and CO2. The catalytic reaction happens in solvent-free conditions. A synergetic effect occur between PVA and KI which considerably increases the reaction yield. This binary catalytic system is mainly suitable for mono-substituted terminal epoxides. In the optimized reaction condition, over 90% reaction yield can be achieved. The binary catalyst is reusable and can be recycled at least five times without significant loss of the catalytic activity. The PVA hydrolysis degree affect the catalytic activity as well. A possible mechanism of synergetic effect of the binary system was proposed. PVA and KI may form a non-toxic, low cost, recyclable, highly-efficiency catalyst for fixing CO2 through cycloaddition with epoxides.
Highly efficient 3d/4d-4f coordination polymer catalysts for carbon dioxide fixation into cyclic carbonates
Wang, Gang,Xu, Cong,Wang, Li,Liu, Weisheng
, p. 12711 - 12717 (2018)
Two novel highly efficient 3d/4d-4f one-dimensional (1D) double-chain coordination polymer catalysts with unique structures were synthesized for the first time. An X-ray single crystal structure analysis revealed that the two compounds are isomorphous and have a 1D metal-organic network coordination polymer structure. Both compounds also showed significant thermal stability and their structures remained stable up to 325 °C. The reaction conditions, type of substrate, amount of catalyst and its catalytic mechanism were investigated. The catalysts ([Dy2M2L4 (OAc)2 (MeOH)5 (H2O)]) (M = Zn, Cd) exhibited excellent catalytic activity in the cycloaddition of CO2 and styrene oxide (C8H8O, SO). High product yields, high selectivity, and the highest turnover frequency (TOF) of 28 400 h-1 were achieved. Additionally, the catalysts can significantly enhance the application of the present types of 3d/4d-4f catalysts in catalysis for transformations involving the fixation of CO2.
A nona-vacant Keggin-type tricarbonyl rhenium derivative {[PMo3O16][Re(CO)3]4}5- and its catalytic performance for CO2 cycloaddition reactions
Huo, Zhiyuan,Guo, Jipeng,Lu, Jingkun,Xu, Qiaofei,Ma, Pengtao,Zhao, Juan,Zhang, Dongdi,Niu, Jingyang,Wang, Jingping
, p. 69006 - 69009 (2015)
A nona-vacant Keggin-type tricarbonyl rhenium derivative [(NH4)5]{[PMo3O16][Re(CO)3]4}·1.5H2O was obtained and characterized. Its frontier orbitals were computed by density functional theory (DFT) calculations. Furthermore, it could act as a Lewis acid catalyst and promote the conversion of CO2 to cyclic carbonate under mild reaction conditions with pyrrolidinium bromide as a co-catalyst.
A tricarbonyl rhenium(I) complex with a pendant pyrrolidinium moiety as a robust and recyclable catalyst for chemical fixation of carbon dioxide in ionic liquid
Wong, Wing-Leung,Cheung, Kwong-Chak,Chan, Pak-Ho,Zhou, Zhong-Yuan,Lee, Kam-Han,Wong, Kwok-Yin
, p. 2175 - 2177 (2007)
A novel Re(I) complex covalently anchored with a pyrrolidinium moiety was successfully synthesized and used as an efficient and recyclable catalyst in the cycloaddition of CO2 with epoxides under mild reaction conditions to give excellent isolated yield and selectivity of cyclic carbonates in pyrrolidinium ionic liquid. The Royal Society of Chemistry.
Remarkably efficient catalysts of amidine hydroiodides for the synthesis of cyclic carbonates from carbon dioxide and epoxides under mild conditions
Aoyagi, Naoto,Furusho, Yoshio,Endo, Takeshi
, p. 240 - 241 (2012)
Hydroiodides of amidines effectively catalyzed the reaction of CO 2 and epoxides under mild conditions such as ordinary pressure and ambient temperature, and the corresponding 5-membered cyclic carbonates were obtained in moderate to high yields.
Cyclic carbonate formation from carbon dioxide and oxiranes in tetrabutylammonium halides as solvents and catalysts
Calo, Vincenzo,Nacci, Angelo,Monopoli, Antonio,Fanizzi, Antonello
, p. 2561 - 2563 (2002)
(Matrix presented) Epoxides dissolved in molten tetralkylammonium salts bearing halides as counterions are converted into cyclic carbonates under atmospheric pressure of carbon dioxide. The reaction rate depends on the nucleophilicity of the halide ion as well as the structure of the cation.
Succinimide-KI: An efficient binary catalyst system for mild, solvent-free cycloaddition of CO2 to epoxides
Li, Qingshuo,Chang, Haibo,Li, Runming,Wang, Hongxia,Liu, Jichun,Liu, Shanhu,Qiao, Congzhen,Lin, Tong
, p. 111 - 117 (2019)
In this study, we have for the first time demonstrated that succinimide (SI)-KI is an efficient catalyst system to synthesize propylene carbonate (PC) from carbon dioxide (CO2) and propylene oxide (PO) at a solvent-free condition. A synergistic effect was observed between SI and KI that largely increased the reaction yield. It enabled the cycloaddition reaction to take place at 70 °C under a low pressure (0.4 MPa) for only 4 h, with a PC yield as high as 97.5%. The overall condition is milder than the reaction catalyzed by most of the other KI involved co-catalyst systems reported in literatures. The excellent catalytic ability was explained by the increased KI solubility in PO due to the presence of SI and the weak acidity of NH in SI which can be enhanced by KI. A reaction mechanism was proposed based on a reaction kinetics study. SI-KI was applicable to cycloaddition of CO2 with other epoxides. It may offer an inexpensive, environmentally-friendly route to synthesis of propylene carbonate from CO2.
Phosphorus-based bifunctional organocatalysts for the addition of carbon dioxide and epoxides
Werner, Thomas,Büttner, Hendrik
, p. 3268 - 3271 (2014)
Bifunctional phosphonium salts were synthesized and employed as organocatalysts for the atom efficient synthesis of cyclic carbonates from CO2 and epoxides for the first time. These catalysts were obtained in high yields by a modular, straightforward one-step synthesis. The hydrogen-bond donating alcohol function in the side chain leads to a synergistic effect accelerating the catalytic reaction. The desired cyclic carbonates are obtained in high yields and selectivity under solvent-free reaction conditions without the use of any co-catalyst. Under optimized reaction conditions various epoxides were converted to the corresponding cyclic carbonates in excellent yields. The products were obtained analytically pure after simple filtration over a silica gel pad. This protocol is even applicable for a multigram reaction scale. Moreover, the catalysts could be easily recovered and reused up to five times.
Hexanuclear 3d-4f complexes as efficient catalysts for converting CO2 into cyclic carbonates
Gao, Guoshu,Wang, Li,Zhang, Ruilian,Xu, Cong,Yang, Huan,Liu, Weisheng
, p. 3941 - 3945 (2019)
A series of novel hexanuclear 3d-4f complexes formulated as {[Ln2Zn4(μ3-OH)2L4(AcO)2(NO3)2(DMF)2]·2(CH3OH), LnIII = Dy3+ (1), Nd3+ (2), Tb3+ (3)} have been synthesized and characterized. These complexes 1-3 show excellent catalytic performance for the cycloaddition of CO2 and epoxides to obtain cyclic carbonates. The catalytic system has a wide substrate scope with high turnover numbers (9700) and high turnover frequencies (808 h-1) under mild conditions. Additionally, the catalysts could be conveniently prepared on a large scale and recycled.
Imidazolium-based ionic liquid immobilized on functionalized magnetic hydrotalcite (Fe3O4/HT-IM): as an efficient heterogeneous magnetic nanocatalyst for chemical fixation of carbon dioxide under green conditions
Khalifeh, Reza,Zarei, Zeinab,Rajabzadeh, Maryam
, p. 810 - 820 (2021)
A reusable, eco-friendly, long-lived and efficient nanocatalyst, imidazolium-based ionic liquid immobilized on functionalized magnetic hydrotalcite (Fe3O4/HT-IM, IM is known as imidazolium-based melamine), was successfully introduced. The structure of the synthesized nanocatalyst was characterized by several techniques which revealed a plate-like shape with an average particle size of approximately 50 nm and also the presence of acidic sites (site density: 12 mmol g-1). The catalytic activity of Fe3O4/HT-IM was explored in the chemical fixation reaction of carbon dioxide towards the preparation of cyclic carbonates under optimized reaction conditions at 100 °C, 0.7 MPa and 1.6 mol% of the nanocatalyst. This reaction was conducted without using any metal, additive, toxic reagents and solvent/co-catalyst which provides mild and green conditions from the standpoint of green chemistry. Owing to having acidic-basic sites which can simultaneously accelerate the ring-opening of the epoxy ring and incorporation of CO2, this catalyst is attractive and suitable for this reaction. In particular, the prepared catalyst can be easily separated using an external magnetic field and reused over six times without any significant loss in catalytic performance and selectivity. This proves its great potential to be implemented for industrial purposes as a green catalyst. This journal is
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.
