- 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
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(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 %).
- Nakano, Koji,Kamada, Toshihiro,Nozaki, Kyoko
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- New titanium catalysts containing tetrazole for cycloaddition of CO 2 to epoxides
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A series of new half-sandwich titanocene [(η5-C 5H5)TiLCl2] (1) and nonorganometallic titanium complexes [TiLCl3(THF)] (2) and [TiL2Cl2] (3) containing 5-(2-hydroxyphenyl)tetrazole (LH) were synthesized in high yield and fully characterized by various spectroscopic methods and X-ray crystallography. In all complexes, the ligand L acted as a monoanionic bidentate ligand and hydrogen bonding between the oxygen of the tetrahydrofuran and hydrogen of the tetrazolyl unit was observed. In the cycloaddition of CO2 to propylene oxide, complex 3 showed the highest activity among the reported Ti complexes.
- Go, Min Jeong,Lee, Kang Mun,Oh, Chang Hwa,Kang, Yi Young,Kim, So Han,Park, Hyoung Ryun,Kim, Youngjo,Lee, Junseong
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- Exploring the catalytic potential of ZIF-90: Solventless and co-catalyst-free synthesis of propylene carbonate from propylene oxide and CO2
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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.
- Tharun, Jose,Mathai, George,Kathalikkattil, Amal Cherian,Roshan, Roshith,Won, Yong-Sun,Cho, Sung June,Chang, Jong-San,Park, Dae-Won
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- Facile synthesis of glycerol carbonate from glycerol using selenium-catalyzed carbonylation with carbon monoxide
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The commercial production of glycerol has increased considerably for several years, because of its rising inevitable formation as a by-product of biodiesel. For the effective utilization of glycerol, a new synthesis of glycerol carbonate (4-hydroxymethyl-2-oxo-1,3-dioxolane) that is used as solvents and raw material of plastics from glycerol was explored. By combined the selenium-catalyzed carbonylation of slightly excess of glycerol with carbon monoxide and potassium carbonate under 0.1 MPa at 20°C for 4 h in DMF with the oxidation of resulting selenocarbonate salt with molecular oxygen (0.1 MPa, 20 °C) for 2 h, glycerol carbonate was obtained in good yields (83-84%). However, sodium hydride to form sodium alkoxide in situ lowered the yield of glycerol carbonate. Use of triethylamine, 1-methylpyrrolidine, and DBU as bases gave poor results. Furthermore, styrene carbonate was obtained in excellent yield (90%) under similar reaction conditions. The catalytic synthesis of glycerol carbonate was also brought about in the mixed gas atmosphere (carbon monoxide:oxygen = 3:1, 0.1 MPa, 20°C). Glycerol carbonate and styrene carbonate were obtained in reasonable yields (197% and 119%, based on selenium used).
- Mizuno, Takumi,Nakai, Takeo,Mihara, Masatoshi
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- Thermodynamic favorable CO2 conversion via vicinal diols and propargylic alcohols: A metal-free catalytic method
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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.
- Han, Li-Hua,Li, Jing-Yuan,Song, Qing-Wen,Zhang, Kan,Zhang, Qian-Xia,Sun, Xiao-Fang,Liu, Ping
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- Homogeneous and silica-supported zinc complexes for the synthesis of propylene carbonate from propane-1,2-diol and carbon dioxide
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Three organozinc complexes have been synthesised and found to catalyse the carbonylation of propylene glycol with carbon dioxide to form propylene carbonate. A similar tethered organozinc complex was supported onto high loading aminopropyl functionalised hexagonal mesoporous silica and was also found to be catalytically active.
- Comerford, James W.,Hart, Sam J.,North, Michael,Whitwood, Adrian C.
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- Reaction of CO2 with propylene oxide and styrene oxide catalyzed by a chromium(iii) amine-bis(phenolate) complex
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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.
- Dean, Rebecca K.,Devaine-Pressing, Katalin,Dawe, Louise N.,Kozak, Christopher M.
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- Poly(ethylene glycol): An alternative solvent for the synthesis of cyclic carbonate from vicinal halohydrin and carbon dioxide
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Poly(ethylene glycol) (PEG) in this work proved to be an efficient reaction medium for the reaction of vicinal halohydrin with carbon dioxide in the presence of a base to synthesise cyclic carbonates. Notably, PEG-400 as an environmentally friendly solvent exhibits a unique influence on reactivity compared with conventional organic solvents. Various cyclic carbonates were prepared in high yield employing this protocol. The process presented here has potential applications in the industrial production of cyclic carbonates because of its simplicity, cost benefits, ready availability of starting materials, and mild reaction conditions.
- Wang, Jing-Lun,He, Liang-Nian,Dou, Xiao-Yong,Wu, Fang
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- Regioselective functionalization of glycerol with a dithiocarbamate moiety: An environmentally friendly route to safer fungicides
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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.
- De Sousa, Rodolphe,Thurier, Cyril,Len, Christophe,Pouilloux, Yannick,Barrault, Joel,Jerome, Franois
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- Adapting a Wacker-type catalyst system to the palladium-catalyzed oxidative carbonylation of aliphatic polyols
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Polyols, which can be obtained readily from bio-feedstock, are converted efficiently into their corresponding cyclic carbonates by using a Wacker-type Pd/Mn catalyst system. A fine tuned redox cascade is essential in ensuring a high productivity of the Pd catalyst in the oxidative carbonylation reaction. Turnover numbers up to 784 molproduct/molpalladium were achieved.
- Doro, Franco,Winnertz, Patrick,Leitner, Walter,Prokofieva, Angelina,Mueller, Thomas E.
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- An efficient catalyst system at mild reaction conditions containing rare earth metal complexes
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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.
- Wu, Ya,Wang, Wen-Zhen,Wu, Yang,Duan, Yan-Shan,Zhang, Jun-Tao,Yang, Peng-Hui,Ni, Bing-Hua
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- New synthesis of glycerol carbonate from glycerol using sulfur-assisted carbonylation with carbon monoxide
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The glycerol carbonate synthesis from glycerol, which is an inevitable by-product of biodiesel production, was established. By combined sulfurassisted carbonylation of glycerol under 1.0 MPa of carbon monoxide at 80°C in DMF with oxidation by copper bromide(II), a facile synthetic method for glycerol carbonate in good yield was developed.
- Mizuno, Takumi,Nakai, Takeo,Mihara, Masatoshi
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- Propylene carbonate synthesis from propylene glycol, carbon dioxide and benzonitrile by alkali carbonate catalysts
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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%.
- Da Silva,Dayoub,Mignani,Raoul,Lemaire
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- Synthesis of cyclic carbonates from diols and CO2 catalyzed by carbenes
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The synthesis of cyclic carbonates from epoxides and CO2 is a well-established reaction, whereas the synthesis of cyclic carbonates from diols and CO2 is considerably more challenging, and few efficient catalysts are available. Here, we describe heterocyclic carbene catalysts, including one derived from a cheap and efficient thiazolium salt, for this latter reaction. The reaction proceeds at atmospheric pressure in the presence of an alkyl halide and Cs2CO3. Reaction mechanisms for the transformations involved are also proposed.
- Bobbink, Felix D.,Gruszka, Weronika,Hulla, Martin,Das, Shoubhik,Dyson, Paul J.
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- Electrochemical activation of carbon dioxide: Synthesis of organic carbonates
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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.
- Casadei, M. Antonietta,Inesi, Achille,Rossi, Leucio
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- Palladium-catalyzed carbonylation of diols to cyclic carbonates
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The catalytic alkoxycarbonylation of 1,2-diols by (neocuproine) palladium(II) acetate (neocuproine=2,9-dimethyl-1,10-phenanthroline) or palladium(II) acetate/(-)-sparteine using N-chlorosuccinimide as the oxidant affords cyclic carbonates. The oxidative carbonylation of diols proceeds under mild conditions, requiring only 1 atm of carbon monoxide, and produces cyclic carbonates in moderate to good yields. Both 1,2- and 1,3-diols can be carbonylated using (neocuproine)Pd(OAc)2 and sodium dichloroisocyanuric acid, which serves as a competent oxidant and base for this system, to yield 5- and 6-membered cyclic carbonates. Copyright
- Pearson, David M.,Conley, Nicholas R.,Waymouth, Robert M.
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- Economical synthesis of cyclic carbonates from carbon dioxide and halohydrins using K2CO3
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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.
- Hirose, Takuji,Shimizu, Shinsuke,Qu, Shujie,Shitara, Hiroaki,Kodama, Koichi,Wang, Lin
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- An efficient and green transesterification of glycols into cyclic carbonates catalysed by KF/Ca-Mg-Al hydrotalcite
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An efficient, convenient, and environmentally friendly method was developed for the transesterification of glycols into cyclic carbonates catalysed by 5 wt% KF/Ca-Mg-Al hydrotalcite. Using as a model the reaction of glycerol with dimethyl carbonate (DMC), various parameters such as molar ratios, catalyst type and amount, reaction temperature and solvent were studied to optimise the reaction. Then, using the optimal conditions, the formation of the corresponding cyclic carbonates via transesterification of ethylene, propylene and styrene glycols with DMC using KF/Ca-Mg-Al hydrotalcite as solid base catalyst were achieved in good to high yields in short reaction times. The catalyst was conveniently separated and reused for ten cycles without appreciable decrease in its activity.
- Hong, Mei,Gao, Lijing,Xiao, Guomin
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- Facile alkali-assisted synthesis of g-C3N4 materials and their high-performance catalytic application in solvent-free cycloaddition of CO2 to epoxides
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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.
- Xu, Jie,Shang, Jie-Kun,Jiang, Quan,Wang, Yue,Li, Yong-Xin
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- Metal halides supported on mesoporous carbon nitride as efficient heterogeneous catalysts for the cycloaddition of CO2
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Abstract A series of ZnCl2/mp-C3N4 catalysts were prepared through a wet impregnation method using mesoporous g-C3N4 materials as catalytic supports. The physicochemical properties of the ZnCl2/mp-C3N4 catalysts were characterized using several techniques, including N2 adsorption-desorption, X-ray diffraction, Fourier transform infrared, UV-vis diffuse reflectance, and X-ray photoelectron spectroscopy. In the cycloaddition reactions of CO2 with propylene oxide (PO) to propylene carbonate (PC), the ZnCl2/mp-C3N4 materials revealed high catalytic performances at 140 C and 6 h. Furthermore, other metal halides including ZnBr2, CoCl2, FeCl3, NiCl2, and MgCl2 catalysts supported on mp-C3N4 were fabricated and the synthesized catalysts also demonstrated high performances in the catalytic cycloaddition of CO2. A possible catalytic mechanism has been proposed. The mp-C3N4 material served mainly as a basic support to adsorb CO2 whereas the supported metal halides were active sites to promote the activation of PO and realize its transform into PC.
- Xu, Jie,Wu, Fei,Jiang, Quan,Shang, Jie-Kun,Li, Yong-Xin
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- Highly active, binary catalyst systems for the alternating copolymerization of CO2 and epoxides under mild conditions
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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.
- Lu, Xiao-Bing,Wang, Yi
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- Study of the catalytic activity of electrochemically reduced forms of phthalocyanines in the reaction of CO2 with epoxides
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Catalytic activity of electrochemically reduced forms of mono- and diphthalocyanine complexes of transition and rare-earth elements in the reaction of carbon dioxide with epoxides is considerably higher than that of corresponding neutral forms. The catalytic efficiency depends on the nature of the phthalocyanine complex, the method of the catalyst immobilization, and the electrophilicity of epoxide.
- Magdesieva,Milovanov,Lokshin,Klemenkova,Tomilova,Butin,Zefirov
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- Calcium carbide as a dehydrating agent for the synthesis of carbamates, glycerol carbonate, and cyclic carbonates from carbon dioxide
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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.
- Choi, Jun-Chul,Fujitani, Tadahiro,Fukaya, Norihisa,Lin, Xiao-Tao,Sato, Kazuhiko,Yuan, Hao-Yu,Zhang, Qiao
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- Pd/C: An efficient and heterogeneous protocol for oxidative carbonylation of diols to cyclic carbonate
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The present protocol involves highly efficient and practical approach for the synthesis of cyclic carbonate via oxidative carbonylation of diols, glycerol, and its derivatives using Pd/C as a heterogeneous, inexpensive, and recyclable catalyst. The effect of various reaction parameters, such as solvent, base, time, and temperature was investigated and applied for the synthesis of value added cyclic carbonates in a good to excellent yield within shorter reaction time. The developed catalytic system circumvents the use of ligand and dehydrating agent with an additional advantage of palladium catalyst recovery and reuse for up to four consecutive cycles.
- Chavan, Sujit P.,Bhanage, Bhalchandra M.
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- Diphenyl Carbonate: A Highly Reactive and Green Carbonyl Source for the Synthesis of Cyclic Carbonates
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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.
- Baral, Ek Raj,Lee, Jun Hee,Kim, Jeung Gon
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- Regioselective and alternating copolymerization of carbonyl sulfide with racemic propylene oxide
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We report the first example of a regioregular and fully alternating poly (propylene monothiocarbonate) (PPMTC) from the well-controlled copolymerization of two asymmetric monomers, carbonyl sulfide and racemic propylene oxide, using (Salen)CrCl in conjunction with bis(triphenylphosphoranylidene)ammonium chloride. The maximum turnover of frequency of this catalyst system was 332 h-1 at 25 C. The contents of monothiocarbonate and tail-to-head linkages of PPMTC were up to 100% (based on 1H NMR spectra) and 99.0% (based on 13C NMR spectra), respectively. PPMTC samples have number-average molecular weight (Mn) up to 25.3 kg/mol with polydispersity index of 1.41. The very low decomposition temperature of 137 C and high refractive index of 1.63 of PPMTC make it a potential scarifying optical adhesive.
- Luo, Ming,Zhang, Xing-Hong,Du, Bin-Yang,Wang, Qi,Fan, Zhi-Qiang
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- Propylene oxide as a dehydrating agent: Potassium carbonate-catalyzed carboxylative cyclization of propylene glycol with CO2 in a polyethylene glycol/CO2 biphasic system
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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.
- Diao, Zhen-Feng,Zhou, Zhi-Hua,Guo, Chun-Xiang,Yu, Bing,He, Liang-Nian
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- Superbase/cellulose: An environmentally benign catalyst for chemical fixation of carbon dioxide into cyclic carbonates
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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.
- Sun, Jian,Cheng, Weiguo,Yang, Zifeng,Wang, Jinquan,Xu, Tingting,Xin, Jiayu,Zhang, Suojiang
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- Ni and Pd N-confused porphyrin complexes as catalysts for the synthesis of cyclic carbonates from epoxides and CO2
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We have demonstrated the design of a novel bifunctional catalyst that is based on an N-confused tetraphenylporphyrin (NCTPP) motif for the cycloaddition of an epoxide to carbon dioxide via cooperative activation of the epoxide through a Pd(ii) or Ni(ii) metal center and a peripheral benzoate moiety with percent conversions of up to 99% and TON = 7000.
- Dela Cruz, Jay-Ar B.,Ruamps, Mirko,Arco, Susan,Hung, Chen-Hsiung
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- Chemoselective synthesis of asymmetrical carbonate from alcohol and dimethyl carbonate catalyzed by ytterbium(III) triflate
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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.
- Yu, Chuanming,Zhou, Baocheng,Su, Weike,Xu, Zhenyuan
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- Biocompatible and recyclable amino acid binary catalyst for efficient chemical fixation of CO2
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In this work, the cycloaddition reactions of CO2 with various epoxides to form five-membered cyclic carbonates catalyzed by an efficient amino acid based biocompatible catalyst were investigated. It was found that the activity of amino acid could be obviously enhanced in the presence of alkali metal salts, and the l-tryptophan catalytic system was the most efficient among the catalysts employed. Based on the result, a possible mechanism for the synergetic effect of catalyst was proposed. The process reported here represents a simple, ecologically safer, cost-effective route to cyclic carbonates with high product quality, as well as easy catalyst recycling.
- Yang, Zifeng,Sun, Jian,Cheng, Weiguo,Wang, Jinquan,Li, Qian,Zhang, Suojiang
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- Zn-Mg mixed oxide as high-efficiency catalyst for the synthesis of propylene carbonate by urea alcoholysis
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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
- Zhang, Tiantian,Zhang, Bingsheng,Li, Lei,Zhao, Ning,Xiao, Fukui
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- Copolymerization of propylene oxide with carbon dioxide catalyzed by zinc adipate
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Copolymerization of carbon dioxide with propylene oxide in the presence of zinc adipate was studied. The effects of the temperature, nature of the solvent, and catalyst concentration on the molecular weight, molecular-weight distribution, and yields of th
- Sakharov,Il'in,Rusak,Nysenko,Klimov
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- Transition metal complexes with pyrazine amine ligand: Preparation, structure and carbon dioxide copolymerization behavior
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Three complexes [Fe(L)2](ClO4)2 (1)、[Ni(L)2](ClO4)2 (2) and [Co(L)2](ClO4)2 (3) were synthesized by the reaction of N,N’-(4-methylpyridin-2-yl)pyrazine-2,6-
- Wang, Wen-Zhen,Xu, Ya-Chao,Wang, Li,Li, Lei-Lei,Xia, Li,Jia, Xin-Gang,Lee, Gene-Hsiang,Peng, Shie-Ming
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- Highly synergistic effect of ionic liquids and Zn-based catalysts for synthesis of cyclic carbonates from urea and diols
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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.
- Cheng, Weiguo,Deng, Lili,Dong, Li,He, Hongyan,Li, Zengxi,Qian, Wei,Shi, Zijie,Su, Qian,Sun, Wenzhong
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- Effect of liophilicity of catalyst in cyclic carbonate formation by transesterification of polyhydric alcohols
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The effect of catalyst liophilicity is shown in cyclic carbonate formation by transesterification. 1,3-Dichlorodistannoxanes as liophilic transesterification catalysts facilitated cyclic carbonate formation from corresponding 1,2-diols and diethyl carbonate in continuous fashion without isolation of catalyst. Thus 0.5 mol% of catalyst could produce 1,2-glycerol carbonate quantitatively in 2 h with multiple recyclability. The product formed during the reaction was almost quantitative and did not require further purification. Isolation of catalyst at any stage showed retention of its activity and identity.
- Patel, Yogesh,George, Jimil,Pillai, S. Muthukumaru,Munshi, Pradip
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- Self-assembled bimetallic aluminum-salen catalyst for the cyclic carbonates synthesis
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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.
- Abboud, Khalil A.,Hahm, Hyungwoo,Hong, Sukwon,Kim, Seyong,Park, Jongwoo,Seong, Wooyong
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- Catalytic synthesis of propylene carbonate from propylene oxide and carbon dioxide in the presence of rhodium complexes modified with organophosphorus ligands and chitosan
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The reaction between CO2 and propylene oxide to produce propylene carbonate in the presence of rhodium complexes modified with organophosphorus ligands and chitosan has been studied. Highly effective catalysts mediating the reaction with almost a 100% yield and 100% selectivity have been prepared using rhodium compounds modified with triphenylphosphine and chitosan. Pleiades Publishing, Ltd., 2013.
- Korosteleva,Markova,Kolesnichenko,Ezhova,Khadzhiev,Trukhmanova
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- CO2 activation and promotional effect in the oxidation of cyclic olefins over mesoporous carbon nitrides
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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.
- Ansari, Mohd Bismillah,Min, Byung-Hoon,Mo, Yong-Hwan,Park, Sang-Eon
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- THE REACTION OF 1,3,2-DIOXASTANNOLANS WITH DIACYL CHLORIDES: DECARBONYLATION IN THE REACTION WITH OXALYL CHLORIDE
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2,2-Dibutyl-1,3,2-dioxastannolans react with carbonyl chloride to give the corresponding ethylene carbonates, and with malonyl chloride or succinyl chloride to give the oligomeric malonates or succinates.The reaction of oxalyl chloride, however, depends of the number of methyl substituents carried by the carbon atoms of the ring; with none, ethylene oxalate is essentially the only product, but increasing methylation induces the evolution of carbon monoxide and the formation of the ethylene carbonate until, with four methyl substituents, only the carbonate of pinacol, and no oxalate is formed, providing a striking example of the Thorpe-Ingold effect.The mechanism of this decarbonylation is discussed.
- Davies, Alwyn G.,Hua-De, Pan,Hawari, Jalal A. -A.
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- Controlled synthesis of asymmetric dialkyl and cyclic carbonates using the highly selective reactions of imidazole carboxylic esters
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(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.
- Rannard, Steve P.,Davis, Nicola J.
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- One-pot atom-efficient synthesis of bio-renewable polyesters and cyclic carbonates through tandem catalysis
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One-pot synthesis of well-defined bio-renewable polyesters and cyclic carbonates in high yields was successfully realized for the first time by way of a tandem reaction using metal salen complexes as catalysts. This tandem process offered unprecedented opportunities for the atom-efficient production of two relevant compounds. This journal is
- Jia, Fan,Chen, Xiaoyu,Zheng, Yan,Qin, Yusheng,Tao, Youhua,Wang, Xianhong
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- Synthesis of 5-membered cyclic carbonates by oxidative carbonylation of 1,2-diols promoted by copper halides
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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.
- Giannoccaro, Potenzo,Casiello, Michele,Milella, Antonella,Monopoli, Antonio,Cotugno, Pietro,Nacci, Angelo
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- Microwave-assisted one pot-synthesis of amino acid ionic liquids in water: Simple catalysts for styrene carbonate synthesis under atmospheric pressure of CO2
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A novel variety of ionic liquids based on naturally occurring amino acids is expeditiously synthesized in water using microwave energy. The amino acid ionic liquids (AAILs) exhibit eminent catalytic activities towards the synthesis of styrene carbonate from styrene oxide and carbon dioxide at atmospheric pressure. The synergistic interaction of the hydrogen-bonding groups with the nucleophile in the AAIL is believed to be the key factor behind the catalytic cycloaddition. Among the various kinds of AAILs tested, the basic AAILs were found to be the most efficient owing to the presence of extra amino groups that could activate the carbon dioxide molecule by formation of a carbamate salt. The AAILs showed appreciable reusability over four cycles without compromising the selectivity towards styrene carbonate synthesis and hence represents an easily synthesizable series of eco-friendly catalysts for CO2 fixation. This journal is the Partner Organisations 2014.
- Roshan, Kuruppathparambil Roshith,Jose, Tharun,Kim, Dongwoo,Cherian, Kathalikkattil Amal,Park, Dae Won
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- One-pot conversion of CO2 and glycerol to value-added products using propylene oxide as the coupling agent
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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)
- Ma, Jun,Song, Jinliang,Liu, Huizhen,Liu, Jinli,Zhang, Zhaofu,Jiang, Tao,Fan, Honglei,Han, Buxing
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- Versatile boiler ash containing potassium silicate for the synthesis of organic carbonates
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In this study, boiler ash containing potassium silicate (BA 900) and potassium silicate (K2SiO3) were proven to be feasible Lewis acid catalysts for the synthesis of different organic carbonates (glycerol carbonate, ethylene carbonate, and propylene carbonate) from different polyol (glycerol, ethylene glycol, and propylene glycol) feedstocks. In addition, the developed catalytic reaction has the ability to produce propylene carbonate at milder reaction temperatures. BA 900 and K2SiO3 were reusable for three consecutive reaction cycles without the loss of activity. The reusable characteristics of catalysts were confirmed through several characterisation techniques, i.e. XRD, FTIR, XRF, N2 physisorption, FESEM-EDX, and Hammett test. All organic carbonates synthesised had a similar synthetic mechanistic pathway, which involved decomposition of intermediate carbamates into their respective carbonates.
- Indran, Vidhyaa Paroo,Haji Saud, Anisah Sajidah,Maniam, Gaanty Pragas,Yusoff, Mashitah Mohd.,Taufiq-Yap, Yun Hin,Ab. Rahim, Mohd Hasbi
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- Novel chromium (III) complexes with N4-donor ligands as catalysts for the coupling of CO2 and epoxides in supercritical CO2
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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.
- Cuesta-Aluja, Laia,Djoufak, Mary,Aghmiz, Ali,Rivas, Raquel,Christ, Lorraine,Masdeu-Bultó, Anna M.
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- METHOD FOR SUSTAINABLE CHEMICAL FIXATION OF CO2
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A method for sustainable fixation of CO2, is disclosed herein. A sustainable chemical fixation of CO2 into epoxide to form value added product such as cyclic carbonates using bimetallic spinel oxide hollow microspheres as an efficient and recyclable catalyst under solvent free and mild reaction conditions.
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Page/Page column 16
(2021/02/19)
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- 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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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.
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Paragraph 0119-0122; 0128-0130
(2021/05/12)
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- Method for synthesizing cyclic carbonate by using metalloporphyrin ion framework to catalyze urea and dihydric alcohol
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The invention relates to a method for preparing cyclic carbonate by using a metalloporphyrin ion framework catalyst. The method is characterized in that urea and a dihydric alcohol compound are subjected to urea alcoholysis reaction under the catalysis of the catalyst to obtain the cyclic carbonate, wherein the catalyst is a metalloporphyrin ion framework heterogeneous catalyst, and the cyclic carbonate prepared by the method has high yield. The method has the characteristics that compared with a traditional catalyst, the used metalloporphyrin ion framework heterogeneous catalyst has multiple active sites, double active components, high catalytic efficiency and stable performance, is easy to separate and recycle from a reaction solution, and has a relatively high industrial application value.
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Paragraph 0073-0074
(2021/08/28)
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- Direct synthesis of polycarbonate diols from atmospheric flow CO2and diols without using dehydrating agents
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Polymer synthesis with CO2 as a C1 chemical has attracted much attention from the viewpoint of green chemistry. The direct transformation of CO2 and diols into polycarbonate diols is promising as an alternative method to the hazardous phosgene process, however, challenging due to the inert characteristic of CO2 and thermodynamic limitation. Herein, we present the direct synthesis of polycarbonate diols from atmospheric pressure CO2 and α,ω-diols using a heterogeneous CeO2 catalyst and a CO2 flow semi-batch reactor. The target alternating polycarbonate diol from CO2 and 1,6-hexanediol was obtained with high yield (92%) and selectivity (97%) without using any dehydrating agents. Activation of atmospheric pressure CO2 by a CeO2 catalyst and the shift of equilibrium towards the product by removing the coproduced water (gas stripping) are responsible for the high yield. The flow reaction system with a CeO2 catalyst was applicable to the reactions of CO2 and primary mono-alcohols or 1,2-diols, giving the target organic carbonates in high selectivity (>99%).
- Gu, Yu,Nakagawa, Yoshinao,Nakao, Kenji,Suzuki, Kimihito,Tamura, Masazumi,Tomishige, Keiichi
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p. 5786 - 5796
(2021/08/23)
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- Cross-linked, porous imidazolium-based poly(ionic liquid)s for CO2capture and utilisation
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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.
- 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
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supporting information
p. 16452 - 16460
(2021/09/28)
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- Efficient conversion of CO2into cyclic carbonates at room temperature catalyzed by Al-salen and imidazolium hydrogen carbonate ionic liquids
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A novel process for the efficient synthesis of cyclic carbonates from CO2 and epoxides at room temperature in the absence of a solvent has been achieved by using Al-salen complexes as catalysts and imidazolium hydrogen carbonate ionic liquids ([CnCmIm][HCO3]) as cocatalysts. As a halide ion-free cocatalyst, [CnCmIm][HCO3] showed higher catalytic reactivity compared to traditional halogen-containing quaternary ammonium salts (such as (nBu)4NBr) and organic bases. The catalytic system can be used for the cycloaddition of a series of substrates with good to excellent yields at room temperature in the absence of a solvent. Besides, the catalytic system can be easily recycled at least four times without significant loss of catalytic activity. A possible mechanism was proposed, in which Al-salen and carbene activate the epoxides and CO2 respectively.
- Hu, Xingbang,Liu, Jia,Liu, Ying,Yang, Guoqiang,Zhang, Dejin,Zhang, Zhibing
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supporting information
p. 4509 - 4515
(2020/08/10)
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- Biomass-derived Cu/porous carbon for the electrocatalytic synthesis of cyclic carbonates from CO2and diols under mild conditions
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Biomass-derived Cu/porous carbon (Cu/PC) composites were facilely assembled by using a one-pot hydrothermal approach combined with calcination under a N2 atmosphere, and were used for the electrocatalytic synthesis of cyclic carbonates from CO2 and diols at room temperature and normal pressure without any other catalysts. The results show that the Cu/PC composites with large specific surface areas (SBET > 279 m2 g-1) and high pore volumes (Vp > 0.47 cm3 g-1) possess good catalytic activity for CO2 electrocatalytic fixation. The Cu nanoparticles were uniformly dispersed in the PC, resulting in a remarkable increase in the catalytic activity of the composite compared with those of pure PC and Cu sheets. In addition, the Cu content influenced the electrocatalytic activity. Among the materials used, Cu/PC-III was the best cathode as it had a 46.3percent electrosynthesis yield of propylene carbonate, wide application prospects and was suitable for the synthesis of other o-diols. The yield of 4-propyl-1,3-dioxolan-2-one reached 57.8percent. The prepared composites also displayed satisfactory reusability, and the yield was not reduced even after six cycles of use. These results reveal that the composites could be effectively used for the electrosynthesis of cyclic carbonates from CO2 and diols under mild conditions.
- Zhang, Jing-Jie,Li, Shi-Ming,Shi, Yi,Hu, Qiao-Li,Wang, Huan,Lu, Jia-Xing
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supporting information
p. 11817 - 11823
(2020/07/27)
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- Room temperature and normal pressure preparation method of organic carbonate
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The invention relates to the technical field of organic synthesis, and provides a room temperature and normal pressure preparation method of organic carbonate. The method comprises the following steps: introducing carbon dioxide into an imidazole ionic liquid to obtain a mixture; mixing the obtained mixture with alcohol and halogenated hydrocarbon, and carrying out addition-substitution reactionsto obtain organic carbonate. The whole reaction process is carried out at a room temperature under a normal pressure. The activation energy of the reaction is reduced by using imidazole ionic liquid and halogenated hydrocarbon, and finally, organic carbonate is prepared from CO2 at a room temperature under a normal pressure.
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Paragraph 0115-0117
(2020/07/15)
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- Selective Conversion of CO 2 and Switchable Alcohols into Linear or Cyclic Carbonates via Versatile Zinc Catalysis
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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.
- Song, Qing-Wen,Zhao, Qing-Ning,Li, Jing-Yuan,Zhang, Kan,Liu, Ping
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p. 739 - 746
(2019/01/23)
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- 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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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)
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Paragraph 0030; 0039-0040
(2019/07/16)
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- Highly regio- And stereoselective synthesis of cyclic carbonates from biomass-derived polyols: Via organocatalytic cascade reaction
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The cascade reaction of CO2, vicinal diols, and propargylic alcohol, was firstly achieved by dual Lewis base (LB) organocatalytic systems involving LB-CO2 adducts and commercially available organic amines. This methodology could overcome the chemical inertness of CO2, providing an alternative route to various functionalized five-membered cyclic carbonates in moderate to high yields under mild reaction conditions (25 °C, 1.0 atm of CO2). More importantly, this method could also be applied for facile and efficient synthesis of chiral polycyclic carbonates from biomass-derived polyols with complete configuration retention of chiral centers. This study provides an environment-friendly, scalable and cost effective protocol to construct value-added cyclic carbonates with multi-functional groups and chiral centers.
- Zhou, Hui,Zhang, Hui,Mu, Sen,Zhang, Wen-Zhen,Ren, Wei-Min,Lu, Xiao-Bing
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supporting information
p. 6335 - 6341
(2019/12/03)
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- CARBON NITRIDE CATALYSTS FOR CO2 ACTIVATION
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Metal modified 2-D and 3-D tetrazole-based carbon nitride materials, method of making and method of use are described. The materials include a catalytic metal, preferably Fe or Ru, and have a nitrogen to carbon ratio of between 1.36 and 2.35. The materials can be used as a catalyst for oxidation of hydrocarbons using CO2, or a mixture of CO2 and O2, as a mild oxidant.
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Paragraph 0061-
(2019/02/13)
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- Method for synthesizing cyclic carbonate from urea and diol under catalysis of ionic liquid
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The invention provides a method for synthesizing cyclic carbonate from urea and diol under the catalysis of an ionic liquid. The method is characterized in that the cyclic carbonate is synthesized from the urea and diol under the catalysis of a composite catalyst composed of a metal salt and the imidazole ionic liquid under the conditions of a reaction temperature of 100-200 DEG C, a reaction pressure of 5-500 KPa and a reaction time of 1-10 h. The method has the advantages of cheap and easily available raw materials, high catalysis efficiency of the composite catalyst, mild reaction conditions, simple process flow and high industrial application values.
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Paragraph 0088-0090; 0100
(2019/09/14)
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- METHOD FOR PRODUCING AROMATIC NITRILE COMPOUND AND METHOD FOR PRODUCING CARBONATE ESTER
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Provided is a method for regenerating an aromatic amide compound into a corresponding aromatic nitrile compound, the method realizing a dehydration reaction of providing a target compound selectively at a high yield with generation of a by-product being suppressed. Also provided is a method for producing an aromatic nitrile compound that decreases the number of steps of dehydration reaction and significantly improves the reaction speed at a pressure close to normal pressure. Furthermore, the above-described production method is applied to a carbonate ester production method to provide a method for producing carbonate ester efficiently. The above-described objects are achieved by a method for producing an aromatic nitrile compound including a dehydration reaction of dehydrating an aromatic amide compound, in which the dehydration reaction uses diphenylether.
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Paragraph 0113
(2019/07/03)
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- METHOD FOR PRODUCING AROMATIC NITRILE COMPOUND AND METHOD FOR PRODUCING CARBONIC ACID ESTER
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Provided is a method for regenerating an aromatic amide compound into a corresponding aromatic nitrile compound, the method realizing a dehydration reaction of providing a target compound selectively at a high yield, with generation of a by-product being suppressed. Also provided is a method for producing an aromatic nitrile compound that decreases the number of steps of the dehydration reaction and significantly improves the reaction speed even at a pressure close to normal pressure. In addition, the above-described production method is applied to a carbonate ester production method to provide a method for producing a carbonate ester efficiently. The above-described methods are realized by a method for producing an aromatic nitrile compound including a dehydration reaction of dehydrating an aromatic amide compound, in which the dehydration reaction uses, as a solvent, any of 1,2-dimethoxybenzene, 1,3-dimethoxybenzene and 1,3,5-trimethoxybenzene.
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Paragraph 0165-0166
(2020/01/08)
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- Versatile and scalable synthesis of cyclic organic carbonates under organocatalytic continuous flow conditions
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The benchmark route for the preparation of cyclic organic carbonates starts from toxic, volatile and unstable epoxides. In this work, cyclic organic carbonates are prepared according to alternative sustainable and intensified continuous flow conditions from the corresponding 1,2-diols. The process utilizes dimethyl carbonate (DMC) as a low toxicity carbonation reagent and relies on the organocatalytic activity of widely available and cheap organic ammonium and phosphonium salts. Glycerol is selected as a model substrate for preliminary optimization with a library of homogeneous ammonium and phosphonium salts. The nature of the anion dramatically influences the catalytic activity, while the nature of the cation does not impact the reaction. Upon optimization, glycerol carbonate is obtained in 95% conversion and 79% selectivity within 3 min residence time at 180 °C (11 bar) with 3.5 mol% of tetrabutylammonium bromide as the organocatalyst. A straightforward liquid-liquid extraction procedure enables both the purification of glycerol carbonate and the recycling of the homogeneous catalyst. The conditions are amenable to refined and crude bio-based glycerol, although conversions are lower in the latter case. Control experiments suggest that water present in the crude samples induces significant hydrolysis of glycerol carbonate. The reaction conditions are then successfully applied on a wide variety of substrates, affording the corresponding cyclic carbonates in overall good to excellent yields (20 examples, 45-95%). The substrate scope notably encompasses bio-based starting materials such as glycerol ethers and erythritol-derived diols. In-line NMR is featured as a qualitative analytical tool for real-time reaction monitoring. The scalability of this carbonation procedure on glycerol is assessed in a commercial pilot-scale silicon carbide continuous flow reactor of 60 mL internal volume. Glycerol carbonate is obtained in 76% yield, corresponding to a productivity of 13.6 kg per day.
- Gérardy, Romaric,Estager, Julien,Luis, Patricia,Debecker, Damien P.,Monbaliu, Jean-Christophe M.
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p. 6841 - 6851
(2019/12/24)
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- The protonated carboxyl imidazole ionic liquid and method for catalytic synthesis of cyclic carbonate method (by machine translation)
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The invention relates to a protonated carboxyl imidazole ionic liquid, having the structural formula shown below: ; In the formula, n=1, 2, 3 or 4, X is Cl, I or Br. The invention also discloses the use of its catalytic process for synthesizing cyclic carbonate: will be protonated carboxyl imidazole ionic liquid and epoxy compound in accordance with the 1:100 - 500 the molar ratio of the added in a reaction kettle, access CO2 To the pressure is 0.5 - 3.0 mpa, then at a temperature of 90 - 130 °C and constant pressure reaction under the condition of 0.5 - 3.0 h, after the reaction is finished after treatment to obtain the cyclic carbonate. The method of the invention mild reaction conditions, catalytic process does not use any organic solvent and the cocatalyst, is an environment-friendly catalytic reaction process. The method of the invention of simple synthesis technology, high reaction activity of the catalyst. (by machine translation)
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Paragraph 0033-0061
(2018/07/06)
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- Method for synthesizing propylene carbonate
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The invention discloses a method for synthesizing propylene carbonate which comprises the following reaction steps of step 1, oxidation reaction: adding propylene, an oxidant, a nanometer oxide and acetylacetone salt in a reaction kettle, then dissolving a mixture with a solvent, performing stirring reaction for 1-2h, and performing cooling to the room temperature; and step 2, ester cyclization reaction: introducing dry carbon dioxide gas into the reaction kettle, performing stirring reaction for 4-6h under the sealing condition, performing cooling to the room temperature, slowly discharging the unreacted carbon dioxide gas, and performing post-treatment to obtain a propylene carbonate product. As for the method, by using the nanometer oxide and the acetylacetone salt as catalysts to synthesize the propylene carbonate with a one-boiler boiling method, and separation and purification of an intermediate is not needed, so that the synthetic technology is optimized, and the production efficiency is improved.
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Paragraph 0019-0040
(2018/09/12)
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- A 1, 2 - propylene glycol with carbon dioxide synthetic propylene carbonate method (by machine translation)
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The present invention provides a 1, 2 - propylene glycol propylene carbonate with carbon dioxide synthesis method, the method to alkaline ionic liquid as catalyst, acetonitrile as solvent, in accordance with the catalyst with the 1, 2 - propylene glycol in a molar ratio of 0.01 - 0.04, solvent and 1, 2 - propylene glycol weight ratio of 4 - 8 adjuvants, at the reaction temperature of 150 - 180 °C, CO2 The pressure of the 1 - 10 mpa conditions, the reaction time is 24 hours. The invention is characterized in that: the reaction raw material is cheap, simple process; alkaline ionic liquid catalyst catalytic effect is high, the raw material 1, 2 - propylene glycol the highest yields of up to 67.2%. (by machine translation)
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Paragraph 0019; 0022; 0025; 0028; 0031; 0034; 0037; 0040
(2018/06/16)
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- Production of cyclic carbonate
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The purpose of the present invention is to provide a practical method for producing a cyclic carbonate, which is widely used for various applications such as electrolytic solutions for lithium-ion secondary batteries and plastic materials, by a reaction between an epoxide (oxirane) and carbon dioxide, the method giving consideration to the reduction of environmental loads and making it possible to produce said cyclic carbonate with high yield under mild conditions, such as at room temperature and atmospheric pressure. The present invention relates to a method for producing a cyclic carbonate, the method being characterized by reacting an epoxide and carbon dioxide in the presence of an iodine-anion-containing phosphonium salt including a hydrogen atom that can form a hydrogen bond with an oxygen atom in the epoxide.
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Paragraph 0150; 0151
(2017/09/06)
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- Metallic organic frame material based on YbIII pentanuclear molecular structure unit, preparation method and application thereof
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The invention relates to a metallic organic frame material based on a YbIII pentanuclear molecular structure unit, a preparation method and an application thereof. According to the technical scheme, the method comprises the following steps: adding Yb(NO3)3, ligand 5,5'-(4-carboxyl-pyridyl-2,5-bis-substituted)-1,3-phthalic acid, solvent N,N-dimethyl formamide and water into a high-temperature resisting spiral opening glass bottle; stirring for 30 minutes under normal temperature; sealing the container and then putting into an oven; keeping for 4 days under the temperature at 378K; slowly cooling to room temperature, thereby acquiring a colorless transparent block crystal; washing with N,N-dimethyl formamide, filtering and drying, thereby acquiring a target product. The metallic organic frame material based on the YbIII pentanuclear molecular structure unit prepared according to the invention is simple in preparation method and has an excellent size selective catalytic performance for the carbon dioxide cycloaddition reaction of the epoxide.
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Paragraph 0033; 0034; 0035; 0036; 0037-0050; 0052-0055
(2017/07/21)
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- Preparation method of ethylene carbonate (propylene carbonate)
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The invention discloses a preparation method of ethylene carbonate (propylene carbonate), and belongs to a novel method for synthesizing cyclic allyl carbonate. According to the method, alkyl polyamine-carbamate prepared in a lab and ethylene oxide (propylene oxide) carry out reactions in the presence of a catalyst to prepare an organic chemical product namely ethylene carbonate (propylene carbonate) with a high additional valve. Moreover, an absorption solvent (alkyl polyamine) can be obtained. The catalyst has a high activity and selectivity, so the yield of ethylene oxide (propylene oxide) is high and can reach more than 90%. The yield of byproduct (alkyl polyamine) can reach more than 95%. The byproduct (alkyl polyamine) can be recovered to cyclically absorb CO2. The fixed C1 resources are converted into an importation chemical product by the preparation method, the greenhouse effect is effectively relieved; at the same time, the problem of large energy consumption for desorption of CO2 in an organic amine solution is solved, and the recovered byproduct can be used to absorb CO2 circularly.
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Paragraph 0018
(2017/08/27)
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- AgI/TMG-Promoted Cascade Reaction of Propargyl Alcohols, Carbon Dioxide, and 2-Aminoethanols to 2-Oxazolidinones
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Chemical valorization of CO2 to access various value-added compounds has been a long-term and challenging objective from the viewpoint of sustainable chemistry. Herein, a one-pot three-component reaction of terminal propargyl alcohols, CO2, and 2-aminoethanols was developed for the synthesis of 2-oxazolidinones and an equal amount of α-hydroxyl ketones promoted by Ag2O/TMG (1,1,3,3-tetramethylguanidine) with a TON (turnover number) of up to 1260. By addition of terminal propargyl alcohol, the thermodynamic disadvantage of the conventional 2-aminoethanol/CO2 coupling was ameliorated. Mechanistic investigations including control experiments, DFT calculation, kinetic and NMR studies suggest that the reaction proceeds through a cascade pathway and TMG could activate propargyl alcohol and 2-aminoethanol through the formation of hydrogen bonds and also activate CO2.
- Li, Xue-Dong,Song, Qing-Wen,Lang, Xian-Dong,Chang, Yao,He, Liang-Nian
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p. 3182 - 3188
(2017/10/03)
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- Ionic liquids/ZnO nanoparticles as recyclable catalyst for polycarbonate depolymerization
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A useful protocol for waste bis-phenol A-polycarbonates (BPA-PC) chemical recycling is proposed based on a bifunctional acid/basic catalyst composed by nanostructured zinc oxide and tetrabutylammonium chloride (ZnO-NPs/NBu4Cl) in quality of Lewis acid and base, respectively. Retro-polymerization reaction proved to be of general application for several nucleophiles, including water, alcohols, amines, polyols, aminols and polyamines, leading to the complete recovery of BPA monomer and enabling the PC polymer to function as a green carbonylating agent (green phosgene alternative) for preparing carbonates, urethanes and ureas. A complete depolymerization can be obtained in seven hours at 100 °C and ZnO nanocatalyst can be recycled several times without sensible loss of activity. Remarkably, when polycarbonate is reacted with glycerol, it is possible to realize in a single process the conversion of two industrial wastes (BPA-PC and glycerol) into two valuable chemicals like BPA monomer and glycerol carbonate (the latter being a useful industrial solvent and fuel additive).
- Iannone, Francesco,Casiello, Michele,Monopoli, Antonio,Cotugno, Pietro,Sportelli, Maria Chiara,Picca, Rosaria Anna,Cioffi, Nicola,Dell'Anna, Maria M.,Nacci, Angelo
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p. 107 - 116
(2016/12/09)
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- PROCESS FOR PRODUCING DIMETHYL CARBONATE
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A process is provided f or producing dimethyl carbonate with high conversion rate. Alkylene glycol reacts with urea via alcohylysis reaction to produce alkylene carbonate and ammonia. The alkylene carbonate produced reacts with methanol via transesterification reaction to produce dimethyl carbonate. Before the dimethyl carbonate is separated from the mixture, the nitrogen-containing impurities are substantially removed. Unreacted feedstock and catalysts are recycled in the process.
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Paragraph 0066-0078
(2017/03/21)
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- CYCLIC CARBONATE PRODUCTION METHOD
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PROBLEM TO BE SOLVED: To provide a production method for obtaining a cyclic carbonate with a relatively high yield without utilizing high-pressure carbon dioxide and without utilizing any metal catalyst. SOLUTION: A cyclic carbonate production method comprises reacting an epoxy compound represented by the formula (1) with carbon dioxide in the presence of a compound represented by PhCH2-X (Ph is a phenyl group; and X is a halogen atom), a homopolymer of chloromethylstyrene, a copolymer of chloromethylstyrene and styrene, or a chloromethylated polystyrene, so as to obtain a cyclic carbonate represented by the formula (2). (R is a substituted/unsubstituted C6-20 aryl group, a substituted/unsubstituted C1-20 alkyl group, or a substituted/unsubstituted C2-20 alkylene group.) COPYRIGHT: (C)2016,JPOandINPIT
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Paragraph 0032; 0033; 0034
(2017/01/09)
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- Method of preparing dimethyl carbonate through indirect alcoholysis
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The invention discloses a method of preparing dimethyl carbonate through indirect alcoholysis. The method includes the following steps of primary alcoholysis, secondary alcoholysis and filtering separation. According to the method of preparing dimethyl carbonate through indirect alcoholysis, by means of indirect urea alcoholysis, the yield of dimethyl carbonate is effectively increased, the production cycle is shortened, three industrial wastes are not discharged in the preparation process, and clean production is achieved.
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Paragraph 0014
(2017/06/14)
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- Method for simultaneously preparing propylene glycol monomethyl ether and propylene carbonate
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The invention provides a method for preparing propylene glycol monomethyl ether and propylene carbonate. The method is characterized in that epoxypropane, methanol and CO2 are in contact with a catalyst, wherein the catalyst comprises a template-containing titanium silicalite molecular sieve. The method adopts template-containing titanium silicalite molecular sieve as the catalyst in preparation of propylene glycol monomethyl ether and propylene carbonate from epoxypropane, methanol and CO2, so a high epoxypropane conversion rate and high glycol monomethyl ether and propylene carbonate selectivity are obtained through a reaction at a low reaction temperature (being not higher than 160DEG C and even not higher than 120DEG C).
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Paragraph 0144; 0145; 0157; 0158
(2016/10/09)
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- Convenient synthesis of ethylene carbonates from carbon dioxide and 1,2-diols at atmospheric pressure of carbon dioxide
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An efficient and convenient synthesis of ethylene carbonates was achieved by the reaction of carbon dioxide with 1,2-diols in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), followed by treatment with 1-bromobutane. This DBU-promoted transformation proceeded at an atmospheric pressure of carbon dioxide at 25 °C and gave ethylene carbonates in good yields.
- Kitamura, Tsugio,Inoue, Yusuke,Maeda, Taisei,Oyamada, Juzo
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- Method for using ionic liquid catalyst for catalyzing urea and propylene glycol to synthesize propylene carbonate
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The invention relates to a method for using ionic liquid catalyst for catalyzing urea and propylene glycol to synthesize propylene carbonate. Ionic liquid is adopted to catalyze urea and propylene glycol to synthesize propylene carbonate. The process includes pre-reaction, propylene carbonate reactive distillation, catalyst separation and propylene carbonate purification. After being subjected to pre-reaction in a pre-reaction device (1), the ionic liquid, propylene glycol and urea are conveyed to a propylene carbonate reactive distillation column (2) for reactive distillation. Column reactor materials in the propylene carbonate reactive distillation column (2) are conveyed to a catalyst separator (3), light components are conveyed into a propylene carbonate purifying column (4) from the top to be purified, and the ionic liquid is recovered from the bottom. Ammonia gas at the top of the propylene carbonate reactive distillation column (2) is extracted and recovered.
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Paragraph 0013
(2016/10/31)
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- Method for simultaneously preparing propylene glycol and propylene carbonate
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The invention relates to the field of fine chemical engineering, and provides a method for simultaneously preparing propylene glycol and propylene carbonate. The method comprises the step that epoxypropane, water and CO2 make contact with a catalyst, wherein the catalyst comprises a titanium silicalite molecular sieve containing a template agent. According to the method, the titanium silicalite molecular sieve containing the template agent is used as the catalyst in the process of preparing propylene glycol and propylene carbonate from epoxypropane, water and CO2, and a high epoxypropane conversion rate and propylene glycol and propylene carbonate selectivity can be obtained even when a reaction is conducted at lower reaction temperature which is not higher than 160 DEG C or even not higher than 120 DEG C.
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Paragraph 0103-0106
(2017/06/14)
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- Chlorine-Free Synthesis of Organic Alkyl Carbonates and Five- and Six-Membered Cyclic Carbonates
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This report presents a new, one-pot, facile, selective and green method for methoxycarbonylation of alcohols and synthesis of five- and six-membered cyclic carbonates from corresponding alcohols with dimethyl carbonate (DMC) in the presence of molecular sieves without any additional solvent and catalyst. Syntheses of bifunctional structures comprising a six-membered cyclic carbonate with allyl ether and methacrylate groups, respectively, for different polymerization modes, were also achieved and showed reproducibility on up-scaling the processes.
- Pyo, Sang-Hyun,Hatti-Kaul, Rajni
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supporting information
p. 834 - 839
(2016/03/09)
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- Dual catalysis with magnetic chitosan: Direct synthesis of cyclic carbonates from olefins with carbon dioxide using isobutyraldehyde as the sacrificial reductant
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Chitosan coated magnetic nanoparticles were synthesized and used as a support for the immobilization of the cobalt(ii) acetylacetonate complex [Co(acac)2] and quaternary triphenylphosphonium bromide [P+Ph3Br-] targeting -NH2 and -OH moieties located on the surface of chitosan. The synthesized material was used as a catalyst for one pot direct synthesis of cyclic carbonates from olefins via an oxidative carboxylation approach with carbon dioxide using isobutyraldehyde as the sacrificial reductant and molecular oxygen as the oxidant. After the reaction, the catalyst was recovered by applying an external magnet and reused for several runs without significant loss in catalytic activity and no leaching was observed during this course.
- Kumar, Subodh,Singhal, Nikita,Singh, Raj K.,Gupta, Piyush,Singh, Raghuvir,Jain, Suman L.
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p. 11860 - 11866
(2015/06/30)
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- One-step synthesis of dimethyl carbonate from carbon dioxide, propylene oxide and methanol over alkali halides promoted by crown ethers
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Crown ethers (i.e. [2,4]-dibenzo-18-crown-6 (DBC), 18-crown-6, 15-crown-5 and 12-crown-4) show obvious co-catalytic effect for alkali halides catalyzing one-step synthesis of dimethyl carbonate (DMC) from CO2, propylene oxide and methanol. Especially, the DMC yield of KCl catalyst promoted by DBC can increase by more than five times and reach about 40% under mild reaction conditions (i.e., low mole ratio of methanol and epoxieds: 7:3, low initial pressure of CO2: 1.5 MPa, reaction temperature: 140 °C, time: 10 h). The optimized molar ratio of KCl to DBC is 2: 1. Due to the good complexing ability between DBC and K+, KCl and DBC formed an organometallic complex. Actually, DBC can not only promote the reaction rate and equilibrium of cycloaddition and transesterification reactions, but also prevent side reaction. Importantly, DBC can conveniently achieve high recovery ratio and show excellent reusability.
- Li, Lei,Shi, Shikai,Song, Li,Guo, Liping,Wang, Yifei,Ma, Hongxia,Hou, Jie,Wang, Haidong
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p. 231 - 236
(2015/08/03)
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- Low pressure one-pot synthesis of dimethyl carbonate catalyzed by an alkali carbonate
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A mild and efficient protocol for the alkali carbonate-catalyzed one-pot synthesis of dimethyl carbonate (DMC) from epoxide, CO2 and methanol was developed. The reaction conditions for the one-pot synthesis of DMC were investigated. Under the optimized conditions of initial pressure 0.5 MPa, 120°C and catalyst loading of 7.5 mol%, 63.5% yield of DMC was achieved using ethylene oxide as the starting material. A mechanism for the catalysis by the alkali carbonate was proposed.
- Liu, Chun,Zhang, Shaoke,Cai, Baoyi,Jin, Zilin
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p. 1136 - 1141
(2015/07/01)
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