108-32-7Relevant articles and documents
Selective formation of polycarbonate over cyclic carbonate: Copolymerization of epoxides with carbon dioxide catalyzed by a cobalt(III) complex with a piperidinium end-capping arm
Nakano, Koji,Kamada, Toshihiro,Nozaki, Kyoko
, p. 7274 - 7277 (2006)
(Chemical Equation Presented) Sidestepping a cyclic side product: Copolymerization of terminal epoxides with CO2 was investigated by using a cobalt(III) complex bearing a piperidinium end-capping arm and a piperidinyl arm (see scheme; DME = 1,2-dimethoxyethane). The catalyst system can selectively produce copolymers without contaminant formation of cyclic carbonates even at high conversion of the epoxide (> 99 %).
Exploring the catalytic potential of ZIF-90: Solventless and co-catalyst-free synthesis of propylene carbonate from propylene oxide and CO2
Tharun, Jose,Mathai, George,Kathalikkattil, Amal Cherian,Roshan, Roshith,Won, Yong-Sun,Cho, Sung June,Chang, Jong-San,Park, Dae-Won
, p. 715 - 721 (2014)
Reported is the application of ZIF-90, which is a highly porous zeolitic imidazolate framework, as a novel catalyst for the cycloaddition of propylene oxide (PO) with CO2 in the absence of co-catalysts and solvents under moderate reaction conditions. The effects of various reaction parameters were investigated. The activity of ZIF-90 was compared with that of various metal-organic-framework (MOF)-based catalysts for the cycloaddition of PO with CO2. Density functional theory calculations elucidated the role of ZIF-90 in creating a favorable environment for the PO-CO2 cycloaddition reaction. A reaction mechanism for the ZIF-90-catalyzed PO-CO2 cycloaddition on the basis of DFT calculations is proposed and the regeneration of ZIF-90 is discussed.
Thermodynamic favorable CO2 conversion via vicinal diols and propargylic alcohols: A metal-free catalytic method
Han, Li-Hua,Li, Jing-Yuan,Song, Qing-Wen,Zhang, Kan,Zhang, Qian-Xia,Sun, Xiao-Fang,Liu, Ping
, p. 341 - 344 (2020)
Organocatalysis represents a promising field in chemical fixation of CO2. Herein, a facile metal-free strategy was reported for the one-pot preparation of cyclic carbonates and α-hydroxy ketones from vicinal diols, propargylic alcohols and CO2. Wide scope of vicinal diols and propargylic alcohols was demonstrated to be efficient under the DBU-catalyzed conditions. A plausible mechanism was proposed, which included detailed main and side reactions under the metal-free conditions.
Reaction of CO2 with propylene oxide and styrene oxide catalyzed by a chromium(iii) amine-bis(phenolate) complex
Dean, Rebecca K.,Devaine-Pressing, Katalin,Dawe, Louise N.,Kozak, Christopher M.
, p. 9233 - 9244 (2013)
A diamine-bis(phenolate) chromium(iii) complex, {CrCl[O 2NN′]BuBu}2 catalyzes the copolymerization of propylene oxide with carbon dioxide. The synthesis of this metal complex is straightforward and it can be obtained in high yields. This catalyst incorporates a tripodal amine-bis(phenolate) ligand, which differs from the salen or salan ligands typically used with Cr and Co complexes that have been employed as catalysts for the synthesis of such polycarbonates. The catalyst reported herein yields low molecular weight polymers with narrow polydispersities when the reaction is performed at room temperature. Performing the reaction at elevated temperatures causes the selective synthesis of propylene carbonate. The copolymerization activity for propylene oxide and carbon dioxide, as well as the coupling of carbon dioxide and styrene oxide to give styrene carbonate are presented.
Regioselective functionalization of glycerol with a dithiocarbamate moiety: An environmentally friendly route to safer fungicides
De Sousa, Rodolphe,Thurier, Cyril,Len, Christophe,Pouilloux, Yannick,Barrault, Joel,Jerome, Franois
, p. 1129 - 1132 (2011)
We report here a convenient pathway for the direct functionalization of glycerol with a dithiocarbamate moiety. This work opens up a cost-efficient and environmentally friendly route to safer fungicides. It should be noted that whereas functionalization of glycerol usually suffers from a lack of selectivity, we show here that our process is fully regioselective.
An efficient catalyst system at mild reaction conditions containing rare earth metal complexes
Wu, Ya,Wang, Wen-Zhen,Wu, Yang,Duan, Yan-Shan,Zhang, Jun-Tao,Yang, Peng-Hui,Ni, Bing-Hua
, p. 1463 - 1466 (2013)
An efficient rare earthmetal complex-catalyzed cycloaddition reaction of CO2 with propylene oxide using Hdpza (di(2-pyrazyl)amine) as a N-donor ligand has been accomplished in good to excellent yields with high selectivity. The effects of different rare earth metal salts, ligands and reaction conditions were examined. Catalytic reaction tests demonstrated that the incorporation of ErCl3 and Hdpza can significantly enhance the catalytic reactivity of the TBAB (nBu4NBr, tetra-n-butyl ammonium bromide) towards cycloaddition reaction of CO2 and propylene oxide that produce cyclic carbonates under mild conditions without any co-solvent.
Propylene carbonate synthesis from propylene glycol, carbon dioxide and benzonitrile by alkali carbonate catalysts
Da Silva,Dayoub,Mignani,Raoul,Lemaire
, p. 58 - 62 (2012)
The synthesis of propylene carbonate from propylene glycol and carbon dioxide in the presence of various catalysts has been reported. Benzonitrile has been used as both solvent and dehydrating agent. Under optimal conditions, the best results were obtained in the presence of alkali carbonate catalysts. The propylene carbonate yield could reach up to 20% with a propylene-1,2-glycol conversion of 44%.
Electrochemical activation of carbon dioxide: Synthesis of organic carbonates
Casadei, M. Antonietta,Inesi, Achille,Rossi, Leucio
, p. 3565 - 3568 (1997)
Electrochemically activated CO2 reacts, under mild conditions, with primary and secondary alcohols bearing a leaving group at the α-position affording the corresponding cyclic carbonates in high yields; unsubstituted alcohols are converted, after addition of EtI, into the corresponding unsymmetrical ethyl carbonates in moderate to good yields. Tertiary alcohols and phenols are stable to the reagent.
Economical synthesis of cyclic carbonates from carbon dioxide and halohydrins using K2CO3
Hirose, Takuji,Shimizu, Shinsuke,Qu, Shujie,Shitara, Hiroaki,Kodama, Koichi,Wang, Lin
, p. 69040 - 69044 (2016)
A highly simple, economical, and selective synthesis of five-membered cyclic carbonates was achieved by the reaction of CO2 with 1,2-halohydrins in the presence of K2CO3. This method allows the efficient preparation of cyclic carbonates (72-95% yields for monosubstituted cyclic carbonates and 43% for 1,1- and 1,2-disubstituted cyclic carbonates) under mild reaction conditions, atmospheric pressure of CO2 at 30 °C, and not only in dry DMF, but also in commercial "anhydrous" DMF. The reaction mechanism was elucidated using the SEM and XRD data of the by-products, KHCO3 and KBr.
Facile alkali-assisted synthesis of g-C3N4 materials and their high-performance catalytic application in solvent-free cycloaddition of CO2 to epoxides
Xu, Jie,Shang, Jie-Kun,Jiang, Quan,Wang, Yue,Li, Yong-Xin
, p. 55382 - 55392 (2016)
A series of graphitic carbon nitride materials were synthesized using guanidine hydrochloride (GndCl) as a precursor with the aid of alkali treatment. The introduction of alkali successfully enabled GndCl to be transformed into g-C3N4 at much lower calcination temperatures (450-475 °C). The g-C3N4 samples synthesized under various conditions have been characterized by several techniques including XRD, FT-IR, UV-vis, 13C NMR, and XPS spectroscopy. The results confirmed that the alkali could effectively accelerate further condensation of melem-like fragments to g-C3N4. Meanwhile, a possible mechanism of alkali-assisted synthesis of g-C3N4 from GndCl has been proposed. In solvent-free catalytic cycloaddition of CO2 to propylene oxide to propylene carbonate (PC), g-C3N4-NaOH and g-C3N4-KOH materials demonstrated high and stable catalytic performances, affording PC yields of ca. 90% under optimized reaction conditions. Moreover, the activities were superior to those obtained over g-C3N4 prepared without alkali treatment. In addition, the catalytic activity along with preparation method for the present g-C3N4 has also been compared with other reported g-C3N4-based catalysts.
Highly active, binary catalyst systems for the alternating copolymerization of CO2 and epoxides under mild conditions
Lu, Xiao-Bing,Wang, Yi
, p. 3574 - 3577 (2004)
Excellent activity and selectivity in the copolymerization of CO 2 with epoxides at extremely mild temperature and pressure are observed in the presence of binary nucleophile-electrophile catalyst systems based on chiral [(salcy)CoIIIX] complexes and quaternary ammonium salts (see scheme). Completely alternating copolymers are obtained with > 95% head-to-tail linkages.
Calcium carbide as a dehydrating agent for the synthesis of carbamates, glycerol carbonate, and cyclic carbonates from carbon dioxide
Choi, Jun-Chul,Fujitani, Tadahiro,Fukaya, Norihisa,Lin, Xiao-Tao,Sato, Kazuhiko,Yuan, Hao-Yu,Zhang, Qiao
, p. 4231 - 4239 (2020)
Carbon dioxide (CO2) is a nontoxic and inexpensive C1 building block, which can be used for the synthesis of valuable chemicals such as aromatic carbamates from anilines and methanol (MeOH), glycerol carbonate from glycerol, and cyclic carbonates from diols. However, these reactions generate water as the byproduct and suffer from thermodynamic limits, which lead to low yields. Calcium carbide (CaC2) is a renewable chemical, which can be recycled from calcium that is abundant in the Earth's crust. Furthermore, CaC2 rapidly reacts with water. In this work, we used CaC2 as a dehydrating agent for the direct synthesis of carbamates (including polyurethane precursors) from amines, CO2, and MeOH. All reagents were commercially available. In addition, CaC2 was employed for the synthesis of glycerol carbonate from glycerol and CO2 with a zinc catalyst and N-donor ligand. A similar protocol was applied to synthesize cyclic carbonates from diols and CO2.
Diphenyl Carbonate: A Highly Reactive and Green Carbonyl Source for the Synthesis of Cyclic Carbonates
Baral, Ek Raj,Lee, Jun Hee,Kim, Jeung Gon
, p. 11768 - 11776 (2018)
A practical, safe, and highly efficient carbonylation system involving a diphenyl carbonate, an organocatalyst, and various diols is presented herein and produces highly valuable cyclic carbonates. In reactions with a wide range of diols, diphenyl carbonate was activated by bicyclic guanidine 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) as a catalyst, which successfully replaced highly toxic and unstable phosgene or its derivatives while maintaining the desired high reactivity. Moreover, this new system can be used to synthesize sterically demanding cyclic carbonates such as tetrasubstituted pinacol carbonates, which are not accessible via other conventional methods.
Propylene oxide as a dehydrating agent: Potassium carbonate-catalyzed carboxylative cyclization of propylene glycol with CO2 in a polyethylene glycol/CO2 biphasic system
Diao, Zhen-Feng,Zhou, Zhi-Hua,Guo, Chun-Xiang,Yu, Bing,He, Liang-Nian
, p. 32400 - 32404 (2016)
The synthesis of propylene carbonate (PC) from 1,2-propylene glycol (PG) and CO2 was smoothly performed in a PEG800 (polyethylene glycol)/CO2 biphasic system with K2CO3 as a catalyst and propylene oxide (PO) as a dehydrating agent. In the reaction of PG with CO2, PO presumably removes the water produced, and simultaneously generates more PG, both of which shift the thermodynamic control process and thus accelerate the PC synthesis. The PC yield directly from PG and CO2 reached 78% under relatively mild reaction conditions (4 MPa, 120 °C, 10 h). Notably, no additional by-product was detected in this process, resulting in economic benefits and the ease of workup procedure.
Superbase/cellulose: An environmentally benign catalyst for chemical fixation of carbon dioxide into cyclic carbonates
Sun, Jian,Cheng, Weiguo,Yang, Zifeng,Wang, Jinquan,Xu, Tingting,Xin, Jiayu,Zhang, Suojiang
, p. 3071 - 3078 (2014)
An environmentally benign catalytic system consisting of 1,8-diazabicyclo[5.4.0]-undec-7-ene (DBU) and cellulose was developed for CO2 chemical fixation with epoxides under metal-free and halide-free conditions. Due to the dual roles played by DBU and cellulose on the activations of CO2 and epoxide, the reaction could be performed with high activity and selectivity. A possible catalytic cycle for the hydrogen bond assisted ring-opening of epoxide and the activation of CO2 induced by DBU was proposed. The process herein represents a simple, ecologically safe and efficient route for CO2 chemical fixation into high value chemicals. This journal is the Partner Organisations 2014.
Chemoselective synthesis of asymmetrical carbonate from alcohol and dimethyl carbonate catalyzed by ytterbium(III) triflate
Yu, Chuanming,Zhou, Baocheng,Su, Weike,Xu, Zhenyuan
, p. 647 - 653 (2007)
Catalyzed by ytterbium(III) triflate, asymmetrical carbonate can be chemoselectively synthesized from alcohols and dimethyl carbonate (DMC) in moderate to good yield under the mild conditions. Copyright Taylor & Francis Group, LLC.
Zn-Mg mixed oxide as high-efficiency catalyst for the synthesis of propylene carbonate by urea alcoholysis
Zhang, Tiantian,Zhang, Bingsheng,Li, Lei,Zhao, Ning,Xiao, Fukui
, p. 38 - 41 (2015)
Zn/Mg catalysts with different atomic ratios of zinc to magnesium were prepared via urea-precipitation. The products were characterized by XRD, BET, SEM, CO2-TPD, and ICP. Compared with pure ZnO, the mixed oxide possessed appropriate alkaline d
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Peppel
, p. 767,770 (1958)
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Highly synergistic effect of ionic liquids and Zn-based catalysts for synthesis of cyclic carbonates from urea and diols
Cheng, Weiguo,Deng, Lili,Dong, Li,He, Hongyan,Li, Zengxi,Qian, Wei,Shi, Zijie,Su, Qian,Sun, Wenzhong
, (2020)
The development of stable and efficient catalysts is an attractive topic for green chemistry reactions under mild reaction conditions. In order to improve solvent-free synthesis of cyclic carbonates from urea and diols, a binary catalyst systems of Zn-based and different ionic liquids (ILs) were developed and examined in this study. The yield of ethylene carbonate (EC) could reach to 92.2% in the presence of C16mimCl/ZnCl2 catalyst. Through exploring the structure-activity relationships of cation and anion, it was confirmed that a synergistic effect of cation and anion of catalyst had important influences on urea alcoholysis. Additionally, the controlling step of EC synthesis reaction involving the elimination of an ammonia molecule from intermediates had been revealed by in situ FT-IR. This could afford a guided insight for synthesizing cyclic carbonates with high yield. Furthermore, a possible mechanism for the catalytic process was proposed based on DFT and the experimental results via FT-IR, 1H-NMR and 13C NMR analysis, which revealed that not only a probable synergistic effects of cation-anion matters, but also C(2)-H of ILs and Zn2+ played a key role in accelerating the reaction of urea alcoholysis. This catalytic mechanism study is to provide a preliminary basis to develop novel catalysts for cyclic carbonates from urea and diols through a green synthetic pathway.
Self-assembled bimetallic aluminum-salen catalyst for the cyclic carbonates synthesis
Abboud, Khalil A.,Hahm, Hyungwoo,Hong, Sukwon,Kim, Seyong,Park, Jongwoo,Seong, Wooyong
, (2021)
Bimetallic bis-urea functionalized salen-aluminum catalysts have been developed for cyclic carbonate synthesis from epoxides and CO2. The urea moiety provides a bimetallic scaffold through hydrogen bonding, which expedites the cyclic carbonate formation reaction under mild reaction conditions. The turnover frequency (TOF) of the bis-urea salen Al catalyst is three times higher than that of a μ-oxo-bridged catalyst, and 13 times higher than that of a monomeric salen aluminum catalyst. The bimetallic reaction pathway is suggested based on urea additive studies and kinetic studies. Additionally, the X-ray crystal structure of a bis-urea salen Ni complex supports the self-assembly of the bis-urea salen metal complex through hydrogen bonding.
CO2 activation and promotional effect in the oxidation of cyclic olefins over mesoporous carbon nitrides
Ansari, Mohd Bismillah,Min, Byung-Hoon,Mo, Yong-Hwan,Park, Sang-Eon
, p. 1416 - 1421 (2011)
Mesoporous carbon nitrides (MCN) were prepared by a nano-casting method using mesoporous silica as a template with different carbon and nitrogen sources like melamine only (MS-MCN), urea-formaldehyde (UF-MCN) and melamine-glyoxal (MG-MCN). These mesoporous carbon nitride materials possess nitrogen moieties which behave like a CO2-philic surface facilitating oxidation of cyclic olefins by molecular oxygen in the co-presence of CO2 below supercritical conditions. The co-presence of CO2 augmented the conversions of cyclic olefins at low pressures of CO2, depicting a promotional effect. Approaches towards quantification of promotional effects and insights into the promotional aspects have been studied.
Controlled synthesis of asymmetric dialkyl and cyclic carbonates using the highly selective reactions of imidazole carboxylic esters
Rannard, Steve P.,Davis, Nicola J.
, p. 933 - 936 (1999)
(equation presented) A new highly selective synthesis of dialkyl carbonates is described. The procedures rely on the previously unknown selectivity of imidazole carboxylic esters synthesized by the reaction of 1,1′-carbonyldiimidazole with alcohols. The imidazole carboxylic esters of secondary or tertiary alcohols form carbonates through the exclusive reaction with primary alcohols in polyols containing mixtures of primary, secondary, and tertiary hydroxyl groups without the need for protection. Controlled cyclic carbonate formation is also described.
Synthesis of 5-membered cyclic carbonates by oxidative carbonylation of 1,2-diols promoted by copper halides
Giannoccaro, Potenzo,Casiello, Michele,Milella, Antonella,Monopoli, Antonio,Cotugno, Pietro,Nacci, Angelo
, p. 162 - 171 (2012)
Copper halides, CuX2 (X = Cl, Br), promote the oxidative carbonylation of vicinal diols [1,2-ethandiol (1,2-ED), 1,2-propanediol (1,2-PD), 1,2-butanediol (1,2-BD)] into the corresponding 5-membered cyclic carbonates, under CO/O2 (Ptot = 3 MPa; P(O2) = 0.5 MPa), at 373 K, in CH3CN and in the presence of a base as co-catalyst. Under these conditions, however, copper salts catalysts proved to be unstable (max turnover, 21.1 mol/mol), evolving into a pale green, insoluble and inactive material, by reaction with water, by-product of the carbonylation process. Contrarily, by carrying out reactions directly in diol, and using DMF as the base, catalytic systems showed to be stable and efficient. Under these conditions, when approximately 40% of the diol has been converted into carbonate, CO2 begins to be formed, deriving from the CO oxidation promoted by H2O that accumulates in the system. The extent of this side reaction, which lowers the yield of CO into cyclic carbonate, increases with the progress of carbonylation. After a diol conversion of 70%, the oxidation of CO to CO2 becomes the main reaction and prevents the complete carbonylation of the diol. The most probable reaction mechanism is also reported and discussed.
One-pot conversion of CO2 and glycerol to value-added products using propylene oxide as the coupling agent
Ma, Jun,Song, Jinliang,Liu, Huizhen,Liu, Jinli,Zhang, Zhaofu,Jiang, Tao,Fan, Honglei,Han, Buxing
, p. 1743 - 1748 (2012)
The effective conversion of carbon dioxide (CO2) and glycerol is an interesting topic in green chemistry. In this work, we studied the simultaneous transformation of CO2 and glycerol to value-added products using propylene oxide (PO)
Novel chromium (III) complexes with N4-donor ligands as catalysts for the coupling of CO2 and epoxides in supercritical CO2
Cuesta-Aluja, Laia,Djoufak, Mary,Aghmiz, Ali,Rivas, Raquel,Christ, Lorraine,Masdeu-Bultó, Anna M.
, p. 161 - 170 (2014)
New neutral and cationic chromium(III) complexes with N4 Schiff base ligands have been prepared and characterized. These complexes are active catalysts for the cycloaddition of CO2 and styrene oxide in CH 2Cl2 solutions, affording epoxide conversions in a 39-92% range, with encouraging cyclic carbonate yields (up to 63%). It is to notice that the cationic species were significantly more active than their neutral analogs. Addition of tetrabutylammonium halides improved the selectivity toward styrene carbonate (87% yield). Dichloromethane could be avoided using solvent free or supercritical carbon dioxide as a solvent (scCO2) and, moreover, this improved the catalytic activity of the cationic complexes (TOF up to 652 h-1). Using scCO2, these chromium catalysts afforded the rapid and selective formation of cyclic carbonates from the coupling of CO2 to various linear terminal epoxides, such as epichlorydrin, propylene oxide and long chain terminal oxiranes. Coupling of cyclohexene oxide and carbon dioxide led to mixtures of poly(cyclohexene) carbonate and cyclic carbonate depending on the conditions (pressure and co-catalyst/catalyst ratio). Poly(cyclohexene) carbonate was isolated with a productivity 388 g/g Cr. Selective formation of the cyclic cyclohexene carbonate was obtained working under scCO2 conditions.
Cross-linked, porous imidazolium-based poly(ionic liquid)s for CO2capture and utilisation
Al-Maythalony, Bassem A.,Al-Qaisi, Feda'a M.,Assaf, Khaleel I.,Eftaiha, Ala'a F.,Hasan, Areej K.,Melhem, Maryam E.,Qaroush, Abdussalam K.,Usman, Muhammad
supporting information, p. 16452 - 16460 (2021/09/28)
CO2is the most influential greenhouse gas with drastic effects all over the world. Meanwhile, global warming is considered a hot topic to different groups of scientists dealing with the global warming phenomenon. As an alternative to the typically-used scrubbing agent that is heavily used in post-combustion capture technology, namely, monoethanolamine, with its well-known drawbacks, the ionic liquids (ILs) and their corresponding polymers,viz., poly(ionic liquid)s (PILs) have been exploited. In this study, we constructed new imidazolium-based PILs with high surface area fabricated from a 3-(3-(phthalimide)propyl)-1-vinylimidazolium bromide IL-precursor withN-allylphthalimide building blocks, in the presence of divinylbenzene serving as a cross-linker, through a free-radical polymerisation process, and provide their ability for the dual purposes of CO2capture and utilisation. In this context, the chemical structure of the monomers was fully characterised using elemental analysis, nuclear magnetic resonance and attenuated total reflectance-infrared spectroscopy. The polymeric materials were further examined by thermogravimetric analysis, the Brunauer-Emmett-Teller model and scanning electron microscopy. The sorption characteristics of the amine functionalised PILs were measured volumetrically with CO2uptake values up to 0.59 mmol CO2per g sorbent under RTP conditions (25 °C and 1 bar). For CO2utilisation purposes, the molar ratio of the ionic residues within the polymeric scaffold was increased ranging from one- and two- up to four-fold (×1, ×2, ×4), respectively. Remarkably, the polymeric materials showed excellent catalytic activity for the cycloaddition of CO2with epoxides to synthesise cyclic carbonates with almost quantitative conversion at 10 bar CO2and 110 °C.
Acylamino-bridged hexacarboxylic acid ligand, metal organic framework material, and preparation method and application of acylamino-bridged hexacarboxylic acid ligand and metal organic framework material
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Paragraph 0119-0122; 0128-0130, (2021/05/12)
The invention relates to the field of metal organic framework materials, and discloses an acylamino-bridged hexacarboxylic acid ligand, a metal organic framework material and a preparation method and application of the acylamino-bridged hexacarboxylic acid ligand and the metal organic framework material. The acylamino-bridged hexacarboxylic acid ligand has a structure as shown in a formula (I). The method for preparing the acylamino-modified metal organic framework material has the characteristics that the synthesis raw materials are cheap and easy to obtain, the reaction condition is mild, the operation is simple, byproducts are few, and large-scale preparation is easy. The acylamino-modified metal organic framework material provided by the invention has the characteristics of stable property, large specific surface area, easy regulation and control of performance, strong selective CO2 adsorption capacity, high catalytic activity, good catalytic conversion effect and recyclability.
