- CYCLIC CARBONATES OBTAINED BY REACTIONS OF ALKALI METAL CARBONATES WITH EPIHALOHYDRINS.
-
A study has been carried out on the reaction of alkali metal carbonates with epihalohydrins in the presence of cation complexing agents e. g. crown ethers. 3-Glycidyloxypropylene carbonate was found to be formed as the main product of the reaction of epichlorohydrin with potassium carbonate promoted by 18-crown-6. The effect of various epihalohydrins and alkali metal carbonates on the reaction course was examined. It was found that the reaction of potassium hydrogencarbonate with epichlorohydrin gives 4-hydroxymethyl-1,3-dioxolan-2-one. When the reaction of epihalohydrins with potassium carbonates was carried out in the atmosphere of carbon dioxide the products contained linear carbonate linkage apart from cyclic one.
- Rokicki,Kuran
-
-
Read Online
- Catalytic activity of metal organic framework Cu3(BTC) 2 in the cycloaddition of CO2 to epichlorohydrin reaction
-
We demonstrate the novel, catalytic activity of metal organic framework of Cu3(BTC)2 catalysts in the synthesis of chloropropene carbonate from CO2 and epichlorohydrin. The catalysts display moderate epoxide conversions, and moderate selectivities to chloropropene carbonate at 100 °C. No solvents or co-catalysts were required. It is suggested that Lewis acid copper (II) sites in the Cu3(BTC) 2 framework promoted the adsorption of carbon dioxide on the solid surface and its further conversion to the carbonate.
- MacIas, Eugenia E.,Ratnasamy, Paul,Carreon, Moises A.
-
-
Read Online
- A highly augmented, (12,3)-connected Zr-MOF containing hydrated coordination sites for the catalytic transformation of gaseous CO2 to cyclic carbonates
-
A porous Zr-based MOF, [Zr6(BTEB)4(μ3-O)4(μ3-OH)4(H2O)4], which contains partially hydrated, 12-connected {Zr6} nodes and extended carboxylate ligands (BTEB3-), was synthesized and physicochemically characterised. The resulting (12,3)-connected, 3D framework adopts an uncommon llj topology with a large, solvent accessible void volume of ca. 79% of the unit cell volume. The porous structure facilitates the uptake of N2 and activated samples give rise to BET surface areas of >1000 m2 g-1. Furthermore, the porosity and accessibility of Lewis acidic Zr(iv) sites promote the catalytic transformation of gaseous CO2 to cyclic carbonates via cycloaddition reactions using epoxide reactants, whereby solvated MOFs exhibit higher catalytic performance than thermally treated samples.
- Jin, Guanghua,Sensharma, Debobroto,Zhu, Nianyong,Vaesen, Sebastien,Schmitt, Wolfgang
-
-
Read Online
- New reaction of glycidols with oxalyl chloride and phosgene - An approach to cyclic esters
-
2,3-Epoxy alcohols (glycidols) react with carboxylic acid dichlorides to form cyclic esters of 3-chloro-1,2-diols. The reaction proceeds with complete retention of the configuration of the C(2) atom of the initial glycidol and with predominant (but not complete) inversion of the configuration of the C(3) atom in the final heterocycle.
- Bredikhin,Pashagin,Strunskaya,Gubaydullin,Litvinov,Bredikhina
-
-
Read Online
- One-step assembly of a hierarchically porous phenolic resin-type polymer with high stability for CO2 capture and conversion
-
A hierarchically porous phenolic resin-type polymer has been successfully prepared by a solvothermal reaction. Given the relatively high surface area, hierarchical pores, good stability and abundant -OH reactive groups, this polymer exhibits high CO2 adsorption and efficient catalytic conversion for CO2 cycloaddition.
- Ding, Meili,Jiang, Hai-Long
-
-
Read Online
- A green catalysis of CO2 fixation to aliphatic cyclic carbonates by a new ionic liquid system
-
A mixed ionic liquid system has been developed for the efficient catalysis of CO2 addition to aliphatic epoxides without involving any transition metal catalysts or other additives. The ionic liquid integrated with pyridinium and pyrrolidinium groups (1·(Br)3) together with a non-polar ionic liquid (3·(Ntf)2) effectively transformed non-polar aliphatic epoxides to cyclic carbonates by the reaction with CO 2 under mild CO2 pressure (3.0 MPa) and reaction temperature (80 C). The presence of 3·(Ntf)2 remarkably improved the catalytic activity of 1·(Br)3 towards non-polar epoxides by increasing the miscibility of catalyst with the substrates. The mixed ionic liquid system is robust enough to be recycled without any significant loss of catalytic activity. GC-MS studies were performed to reveal the reaction pathways to the cyclic carbonates and a feasible model accounting for the effective CO2 activation in the ionic liquid system was proposed using density functional theory (DFT) calculations.
- Wong, Wing-Leung,Lee, Lawrence Yoon Suk,Ho, Kam-Piu,Zhou, Zhong-Yuan,Fan, Ting,Lin, Zhenyang,Wong, Kwok-Yin
-
-
Read Online
- Highly disordering nanoporous frameworks of lanthanide-dicarboxylates for catalysis of CO2 cycloaddition with epoxides
-
A series of nanoporous [LnIII4(di-nitro-BPDC)4(NO2)3(OH)(H2O)5]·n(methanol) (LnIII ?= ?PrIII, NdIII, SmIII, EuIII, GdIII, PrIII/GdIII and PrIII/EuIII; di-nitro-BPDC2- ?= ?2,2′-dinitrobiphenyl-4,4′-dicarboxylate) was synthesized and characterized. Founded on Lewis acidic LnIII possessing vacant coordination sites and functional groups of di-nitro-BPDC2-, their catalytic activities were evaluated based on the CO2 cycloaddition reactions with epoxides under ambient pressure and solvent-free conditions. Depending on catalytic conditions, satisfying turnover number and turnover frequency of 1106 and 276 h-1, respectively, could be yielded with ≥79(±4)% conversion and 87(±1)% selectivity. The correlation between the catalysis performance and structural factors is proposed on a basis of experimental and computation results. These include the restrained transportation even in the nanoporous framework and crystallographic disorder in the LnIII coordination environment. The excellent robustness of the catalysts, effects of lanthanide contraction, and synergistic activities of the heterometallic PrIII/GdIII and PrIII/EuIII catalysts are also included.
- Chiangraeng, Natthiti,Konno, Takumi,Kuwamura, Naoto,Nimmanpipug, Piyarat,Rujiwatra, Apinpus,Thammakan, Supaphorn
-
-
- In situconstruction of phenanthroline-based cationic radical porous hybrid polymers for metal-free heterogeneous catalysis
-
Rational design of multifunctional radical porous polymers with redox activity for targeted metal-free heterogeneous catalysis is an important research topic. In this work, we reported a new class of phenanthroline-based cationic radical porous hybrid polymers (Phen˙+-PHPs), which were constructed from the Heck reaction between a newly designed dibromo-substituted phenanthroline ionic monomer (iDBPhen) and a rigid building block, octavinylsilsesquioxane (VPOSS). For the first time, the stable phenanthroline-based radical cation was unexpectedly discovered in these polyhedral oligomeric silsesquioxane (POSS)-based porous hybrid polymers, probably undergoingin situreduction of the dicationic monomer iDBPhen during the alkaline reagent K2CO3-involved Heck reaction. The radical characters of the typical porous polymers Phen˙+-PHP-2 and Phen˙+-PHP-2Br were confirmed from the electron paramagnetic resonance (EPR) spectra and X-ray photoelectron spectra (XPS). The chemical structures and porous geometry were fully characterized by a series of advanced technologies. Surprisingly, the metal-free cationic radical polymer Phen˙+-PHP-2 exhibited high heterogeneous catalytic efficiency in the H2O2-mediated selective oxidation of various sulfides to sulfoxides with high yields under mild conditions, owing to the electron-accepting and redox ability of Phen-based dications and radical cations. Moreover, the extended sample Phen˙+-PHP-2Br prepared by post-treatment of Phen˙+-PHP-2 with aqueous HBr was also employed as a metal-free efficient heterogeneous catalyst in the conversion of CO2with epoxides into cyclic carbonates under atmospheric pressure and low temperatures. The remarkable catalytic performance in CO2conversion should be assigned to the synergistic catalysis of POSS-derived Si-OH groups and nucleophilic Br?anions and N active atom-involved Phen cationic radical moieties within Phen˙+-PHP-2Br. These two catalysts can be facilely recovered and reused, also with stable recyclability in the above catalytic reaction systems, achieving the heterogeneous catalytic demands for multipurpose reactions.
- Chen, Guojian,Zhang, Yadong,Liu, Ke,Liu, Xiaoqing,Wu, Lei,Zhong, Hu,Dang, Xuejing,Tong, Minman,Long, Zhouyang
-
supporting information
p. 7556 - 7565
(2021/04/06)
-
- Cross-linked, porous imidazolium-based poly(ionic liquid)s for CO2capture and utilisation
-
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
-
supporting information
p. 16452 - 16460
(2021/09/28)
-
- Method for preparing cyclic carbonate through catalysis of hydrogen bond donor functionalized polymeric ionic liquid
-
The invention provides a preparation method of a hydrogen bond donor functionalized polymerization ionic liquid catalyst, and a method for synthesizing cyclic carbonate by catalyzing CO2 and epoxide with the catalyst. According to the method, an imidazolyl ionic liquid monomer and a hydrogen bond donor monomer are subjected to cross-linking polymerization in proportion to form the polymerized ionic liquid catalyst, the catalyst can efficiently catalyze CO2 and epoxide to be converted into cyclic carbonate under the optimal reaction condition, and the yield can reach 99%. Compared with a traditional catalyst, the polymerization ionic liquid catalyst has the advantages that a hydrogen bond donor and ionic liquid are effectively combined in a free radical polymerization manner to form a heterogeneous catalyst which has the advantages of rich hydrogen bond donor, dispersed active sites, good catalytic effect, simple preparation method, good cycle performance, simple separation and the like, and huge industrial application potential is achieved.
- -
-
Paragraph 0049-0087; 0093-0097
(2021/02/10)
-
- METHOD FOR SUSTAINABLE CHEMICAL FIXATION OF CO2
-
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.
- -
-
Page/Page column 16
(2021/02/19)
-
- 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
-
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.
- -
-
Paragraph 0119-0122; 0128-0130
(2021/05/12)
-
- Highly synergistic effect of ionic liquids and Zn-based catalysts for synthesis of cyclic carbonates from urea and diols
-
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
-
-
- Metal ionic liquid, preparation method thereof, and application of metal ionic liquid in catalyzing cycloaddition reaction of carbon dioxide to prepare cyclic carbonate
-
The invention discloses a metal ionic liquid, a preparation method thereof, and an application of the metal ionic liquid in catalyzing a cycloaddition reaction of carbon dioxide to prepare cyclic carbonate. The metal ionic liquid is prepared by mixing and heating an imidazole ionic liquid and a zinc haloid. The preparation method comprises the following steps: adding various reactants into a reaction kettle according to a feeding ratio, stirring and reacting the reactants at a temperature of 30-90 DEG C for 12-48 h, carrying out extraction separation multiple times by using a small amount of dichloromethane, carrying out rotary evaporation on the obtained extract liquor by using a vacuum rotary evaporator at 50 DEG C to remove dichloromethane and most of water in the extract liquor, then putting the extract liquor into a vacuum drying oven, and drying the extract liquor at 80 DEG C for 48 h to remove residual water in order to obtain the clear and transparent metal ionic liquid. The metal ionic liquid not only can be used as a good solvent for the cycloaddition reaction of carbon dioxide, but also has excellent catalytic activity and selectivity for catalyzing epoxide and carbon dioxide to generate cyclic carbonate.
- -
-
Paragraph 0064-0080
(2020/03/29)
-
- Highly regio- And stereoselective synthesis of cyclic carbonates from biomass-derived polyols: Via organocatalytic cascade reaction
-
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
-
supporting information
p. 6335 - 6341
(2019/12/03)
-
- Laminaria digitata and palmaria palmata seaweeds as natural source of catalysts for the cycloaddition of CO2 to Epoxides
-
Seaweed powder has been found to act as an effective catalyst for the fixation of CO2 into epoxides to generate cyclic carbonates under solvent free conditions. Model background reactions were performed using metal halides and amino acids typically found in common seaweeds which showed potassium iodide (KI) to be the most active. The efficacy of the seaweed catalysts kelp (Laminaria digitata) and dulse (Palmaria palmata) was probed based on particle size, showing that kelp possessed greater catalytic ability, achieving a maximum conversion and selectivity of 63.7% to styrene carbonate using a kelp loading of 80% by weight with respect to epoxide, 40 bar of CO2, 120?C for 3 h. Maximizing selectivity was difficult due to the generation of diol side product from residual H2O found in kelp, along with a chlorinated by-product thought to form due to a high quantity of chloride salts in the seaweeds. Data showed there was loss of organic matter upon use of the kelp catalyst, likely due to the breakdown of organic compounds and their subsequent removal during product extraction. This was highlighted as the likely cause of loss of catalytic activity upon reuse of the Kelp catalyst.
- Comerford, James W.,Gray, Thomas,Lie, Yann,Macquarrie, Duncan J.,North, Michael,Pellis, Alessandro
-
-
- Method for synthesizing cyclic carbonate from urea and diol under catalysis of ionic liquid
-
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.
- -
-
Paragraph 0091-0093; 0100
(2019/09/14)
-
- Cyclic carbonate preparation method
-
The invention provides a cyclic carbonate preparation method which includes the step: catalyzing synthesis of cyclic carbonate by the aid of catalysts, wherein the catalysts are amino acrylate ionic liquid polymer heterogeneous catalysts. Cyclic carbonate prepared by the method has high selectivity and transformation rate, and the purity of the obtained cyclic carbonate can reach 99.9mol%. Compared with a traditional method for preparing the cyclic carbonate, the preparation method has the advantages that the used ionic liquid polymer catalysts have more active sites and high catalytic efficiency, are stable, not easy to decompose, simple in preparation process, small in addition amount and easily separated from liquid phases, have high industrial application values and the like.
- -
-
Paragraph 0049; 0050; 0051; 0052; 0090; 0091; 0092
(2019/01/23)
-
- Preparation method and application of bis(N-(4-carboxy)phenyl)phthalimide zinc complex catalyst
-
The invention discloses a preparation method of a bis(N-(4-carboxy)phenyl)phthalimide zinc complex catalyst. The preparation method includes reacting zinc acetate with bis(N-(4-carboxy)phenyl)perylenebisimide, triethylamine, water and N,N'-dimethylamide in a beaker, performing filtration after reaction, and slowly evaporating the filtrate to obtain a crystal of the bis(N-(4-carboxy)phenyl)phthalimide zinc complex catalyst. The preparation method has a simple reaction process, the obtained product has high purity, and the post-treatment is simple. In a carbon dioxide cycloaddition reaction under normal pressure, the conversion rate is as high as 97.5%, and the selectivity is as high as 97.9%.
- -
-
Paragraph 0048; 0049; 0050; 0051; 0052
(2019/06/30)
-
- The protonated carboxyl imidazole ionic liquid and method for catalytic synthesis of cyclic carbonate method (by machine translation)
-
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)
- -
-
Paragraph 0033; 0063; 0064
(2018/07/06)
-
- A General Catalytic Method for Highly Cost- and Atom-Efficient Nucleophilic Substitutions
-
A general formamide-catalyzed protocol for the efficient transformation of alcohols into alkyl chlorides, which is promoted by substoichiometric amounts (down to 34 mol %) of inexpensive trichlorotriazine (TCT), is introduced. This is the first example of a TCT-mediated dihydroxychlorination of an OH-containing substrate (e.g., alcohols and carboxylic acids) in which all three chlorine atoms of TCT are transferred to the starting material. The consequently enhanced atom economy facilitates a significantly improved waste balance (E-factors down to 4), cost efficiency, and scalability (>50 g). Furthermore, the current procedure is distinguished by high levels of functional-group compatibility and stereoselectivity, as only weakly acidic cyanuric acid is released as exclusive byproduct. Finally, a one-pot protocol for the preparation of amines, azides, ethers, and sulfides enabled the synthesis of the drug rivastigmine with twofold SN2 inversion, which demonstrates the high practical value of the presented method.
- Huy, Peter H.,Filbrich, Isabel
-
supporting information
p. 7410 - 7416
(2018/04/30)
-
- Amino-functionalized pyrazole ion liquid and method for catalytic synthesis of cyclic carbonate by utilizing same
-
The invention relates to a method for catalytic synthesis of cyclic carbonate by utilizing amino-functionalized pyrazole ion liquid. The method comprises the following steps: adding the amino-functionalized pyrazole ion liquid and an epoxy compound into a reaction kettle according to a molar ratio of 1:(70 to 500), introducing CO2 till pressure in the reaction kettle is 0.5-3.0MPa, then carrying out constant-temperature and constant-pressure reaction for 0.5-5 hours under the condition that the temperature is 80-130 DEG C, and after the reaction is ended, treating to obtain the cyclic carbonate. The amino-functionalized pyrazole ion liquid has the following structural formula shown in the description, wherein n is equal to 1 or 2, and R is CH3 or C2H5. The method has the advantages of simple synthetic process, high catalyst activity, mild catalytic condition, green and environment-friendly effects, no use of other solvents and cocatalysts, no metal contained in the catalyst, and the like.
- -
-
Paragraph 0021-0022; 0023-0044; 0047-0048
(2018/07/30)
-
- Diphenyl Carbonate: A Highly Reactive and Green Carbonyl Source for the Synthesis of Cyclic Carbonates
-
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
-
p. 11768 - 11776
(2018/09/27)
-
- An in situ formed Ca2+-crown ether complex and its use in CO2-fixation reactions with terminal and internal epoxides
-
Herein we report an efficient catalytic system based on readily available calcium iodide and 18-crown-6 ether for the atom economical addition of CO2 to epoxides. 1H NMR experiments revealed the selective in situ formation of a crown ether complex. This catalyst allows the conversion of various terminal epoxides under 1 atm CO2 pressure even at room temperature. Remarkably, a broad range of internal epoxides with various substitution patterns and substituents were smoothly converted which confirms the high efficiency and capability of the protocol. Notably, most of the internal carbonates were synthesized in high yields and diastereoselectivities of up to ≥99%. Furthermore, this system operates under solvent-free conditions without any co-catalysts e.g. onium salts.
- Steinbauer,Spannenberg,Werner
-
supporting information
p. 3769 - 3779
(2017/08/26)
-
- A pyrazole ionic liquid and utilizing its catalytic process for synthesizing cyclic carbonate (by machine translation)
-
The invention relates to a pyrazole ionic liquid, the pyrazole ionic liquid is 1, 2 - diethyl pyrazole Iodized salt, its structural formula as follows: . The invention also discloses the use of the pyrazole ionic liquid catalytic process for synthesizing cyclic carbonate, its to epoxy compound and CO2 As raw materials, the use of pyrazole ionic liquid 1, 2 - diethyl pyrazole Iodized salt as catalyst, in pressure 0.5 - 5 mpa, temperature 90 °C -150 °C reaction under the condition of 1 - 5 H-synthesizing cyclic carbonate. The method of the invention the process is simple, mild reaction conditions, the activity of the catalyst is high and is in a solid state at room temperature, has overcome the traditional ion liquid great increase of viscosity of the difficult problem of use, is an environment-friendly catalytic process, the obtained cyclic carbonate the highest yield is 96.2%. (by machine translation)
- -
-
Paragraph 0016; 0017; 0018; 0019; 0020-0035; 0038-0039
(2017/08/30)
-
- Protonated pyrazole ionic liquid, and method used for catalytic synthesis of cyclic carbonate with protonated pyrazole ionic liquid
-
The invention provides a protonated pyrazole ionic liquid, and a method used for catalytic synthesis of cyclic carbonate with the protonated pyrazole ionic liquid. The structure formula of the protonated pyrazole ionic liquid is disclosed in the invention. According to the method, the protonated pyrazole ionic liquid and an epoxy compound are introduced into a high temperature reaction kettle at a molar ratio of 1:10-300, CO2 is introduced into the high temperature reaction kettle until the pressure in the high temperature reaction kettle is increased to 1 to 4MPa, constant temperature constant pressure reaction is carried out for 1 to 4h at 100 to 150 DEG C, and cyclic carbonate is obtained via post-treatment. Compared with the prior art, the method possesses following advantages: reaction conditions are mild, catalyst activity is high, no organic solvent is used in the process, and the catalysis reaction process is friendly to the environment.
- -
-
Paragraph 0038; 0043; 0045-0047; 0049; 0051; 0053; 0055
(2017/08/30)
-
- Economical synthesis of cyclic carbonates from carbon dioxide and halohydrins using K2CO3
-
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
-
p. 69040 - 69044
(2016/08/05)
-
- Iron-Catalyzed Synthesis of Five-Membered Cyclic Carbonates from Vicinal Diols: Urea as Sustainable Carbonylation Agent
-
A new iron-catalyzed synthesis of cyclic carbonates from the corresponding vicinal diols and urea is described. This straightforward transformation allows for the preparation of a variety of five-membered carbonates by employing an inexpensive and environmentally benign iron salt as the catalyst. The use of readily available feedstocks such as urea and polyols makes this a sustainable process. As ammonia is formed as the only stoichiometric byproduct, this process can also be characterized by its high atom economy.
- Pe?a-López, Miguel,Neumann, Helfried,Beller, Matthias
-
supporting information
p. 3721 - 3727
(2016/08/16)
-
- Ionic Polymer Microspheres Bearing a CoIII-Salen Moiety as a Bifunctional Heterogeneous Catalyst for the Efficient Cycloaddition of CO2and Epoxides
-
We report a unique strategy to obtain the bifunctional heterogeneous catalyst TBB-Bpy@Salen-Co (TBB=1,2,4,5-tetrakis(bromomethyl)benzene, Bpy=4,4'-bipyridine, Salen-Co=N,N'-bis({4-dimethylamino}salicylidene)ethylenediamino cobalt(III) acetate) by combining a cross-linked ionic polymer with a CoIII-salen Schiff base. The catalyst showed extra high activity for CO2fixation under mild, solvent-free reaction conditions with no requirement for a co-catalyst. The synthesized catalyst possessed distinctive spherical structural features, abundant halogen Br-anions with good leaving group ability, and accessible Lewis acidic Co metal centers. These unique features, together with the synergistic role of the Co and Br-functional sites, allowed TBB-Bpy@Salen-Co to exhibit enhanced catalytic conversion of CO2into cyclic carbonates relative to the corresponding monofunctional analogues. This catalyst can be easily recovered and recycled five times without significant leaching of Co or loss of activity. Moreover, based on our experimental results and previous work, a synergistic cycloaddition reaction mechanism was proposed.
- Leng, Yan,Lu, Dan,Zhang, Chenjun,Jiang, Pingping,Zhang, Weijie,Wang, Jun
-
p. 8368 - 8375
(2016/06/13)
-
- CYCLIC CARBONATE PRODUCTION METHOD
-
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
- -
-
Paragraph 0032; 0033; 0034
(2017/01/09)
-
- MODIFIED POROUS HYPERCROSSLINKED POLYMERS FOR CO2 CAPTURE AND CONVERSION
-
The present disclosure describes a process for making a hyperporous material for capture and conversion of carbon dioxide. The process comprises the steps a first self-polymerisation of benzyl halides via Friedel-Crafts reaction. In the second step the obtained hypercrosslinked polymer is further coupled with an amine or heterocyclic compound having at least one nitrogen ring atom. The invention also relates to the material obtained to the process and its use in catalytic reactions, for instance the conversion of epoxides to carbonates. Salt-modified porous hypercrosslinked polymers obtained according to the invention show a high BET surface (BET surface area up to 926m2/g) combined with strong CO2 capture capacities (14.5 wt%). The nitrogen compound functionalized hypercrosslinked polymer catalyst shows improved conversion rates compared to known functionalized polystyrene materials and an excellent recyclability. A new type of imidazolium salt modified polymers shows especially high capture and conversion abilities. Carbonates can be produced in high yields according to the inventive used of the obtained polymers.
- -
-
Page/Page column 19
(2016/10/31)
-
- METHOD OF CONVERTING ALCOHOL TO HALIDE
-
The present invention relates to a method of converting an alcohol into a corresponding halide. This method comprises reacting the alcohol with an optionally substituted aromatic carboxylic acid halide in presence of an N-substituted formamide to replace a hydroxyl group of the alcohol by a halogen atom. The present invention also relates to a method of converting an alcohol into a corresponding substitution product. The second method comprises: (a) performing the method of the invention of converting an alcohol into the corresponding halide; and (b) reacting the corresponding halide with a nucleophile to convert the halide into the nucleophilic substitution product.
- -
-
Page/Page column 51; 179; 180
(2017/01/02)
-
- Dual catalysis with magnetic chitosan: Direct synthesis of cyclic carbonates from olefins with carbon dioxide using isobutyraldehyde as the sacrificial reductant
-
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.
-
p. 11860 - 11866
(2015/06/30)
-
- Synthesis of the Multinuclear Cobaloxime Complexes via Click Chemistry as Catalysts for the Formation of Cyclic Carbonates from Carbon Dioxide and Epoxides
-
In this study, the structurally similar multinuclear cobaloxime complexes based on dioxime ligands were synthesized and characterized as trinuclear complexes with respect to varied axial groups. The multinuclear cobaloxime complexes were characterized by 1H, 13C-NMR, FT-IR, UV-Vis, LC-MS spectra, melting point and magnetic susceptibility measurements. These multinuclear cobaloxime complexes have been successfully applied to the synthesis of cyclic carbonates from CO2 and epoxides under optimized conditions and without using any solvent. All multinuclear cobaloxime complexes obtained by click chemistry are good catalysts for the cycloaddition of CO2 to different epoxides in the presence of pyridine as a co-catalyst. Additionally, the effects of epoxides, bases, temperature, pressure, and time on the yield of cyclic carbonates were investigated.
- Kilic, Ahmet,Keles, Armagan,Aytar, Emine,Durgun, Mustafa,Ulusoy, Mahmut
-
p. 1665 - 1674
(2015/12/01)
-
- Pd/C: An efficient and heterogeneous protocol for oxidative carbonylation of diols to cyclic carbonate
-
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.
-
supporting information
p. 1199 - 1202
(2014/02/14)
-
- Microwave-assisted one pot-synthesis of amino acid ionic liquids in water: Simple catalysts for styrene carbonate synthesis under atmospheric pressure of CO2
-
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
-
p. 963 - 970
(2014/04/03)
-
- Biocompatible and recyclable amino acid binary catalyst for efficient chemical fixation of CO2
-
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
-
-
- METAL PORPHYRIN COMPLEX, METHOD FOR PRODUCING SAME, CARBON DIOXIDE IMMOBILIZATION CATALYST COMPRISING SAME, AND METHOD FOR PRODUCING CYCLIC CARBONIC ACID ESTER.
-
There is provided a metalloporphyrin complex represented by general formula (1): wherein M is a metal; A1 to A4 are independently of each other a substituent represented by general formula (2): ????????-D-E X-?????(2) wherein D is a divalent organic group having 1 to 20 carbon atoms; E+ is a quaternary ammonium group or quaternary phosphonium group having 3 to 60 carbon atoms; and X is a halogen atom. There is thus provided a metalloporphyrin complex which, when used as a carbon dioxide fixation catalyst, exhibits high catalytic activity, has a small environmental burden and can be easily synthesized.
- -
-
Paragraph 0112; 0113; 0115
(2014/08/06)
-
- METHODS AND SYSTEMS FOR THE FORMATION OF CYCLIC CARBONATES
-
Described herein are inventive methods for synthesis of cyclic carbonates from C02 and epoxide. In some embodiments, the methods are carried out in the presence of a catalyst comprising an electrophilic halogen. In some embodiments, the methods are carried out in a flow reactor.
- -
-
Page/Page column 30; 32
(2013/12/03)
-
- Influence of temperature and pressure on cyclic carbonate synthesis catalyzed by bimetallic aluminum complexes and application to overall syn -bis-hydroxylation of alkenes
-
The effect of moderate temperatures (22-100 °C) and pressures (1-10 bar) on the synthesis of cyclic carbonates from epoxides and carbon dioxide catalyzed by a combination of bimetallic aluminum complexes and tetrabutylammonium bromide is investigated. The combined bimetallic complex and tetrabutylammonium bromide catalyst system is shown to be an order of magnitude more active than the use of tetrabutylammonium bromide alone at all temperatures and pressures studied. At the higher temperatures and pressures used, disubstituted epoxides become substrates for the reaction and it is shown that reactions proceed with retention of the epoxide stereochemistry. This allowed a route for the overall syn-bis-hydroxylation of alkenes to be developed without the use of hazardous metal based reagents. At higher pressures it is also possible to use compressed air as the carbon dioxide source.
- Beattie, Christopher,North, Michael,Villuendas, Pedro,Young, Carl
-
p. 419 - 426
(2013/03/13)
-
- Branched cationic polyurethane prepared by polyaddition of chloromethylated five-membered cyclic carbonate and diethylenetriamine in molten salts
-
A branched cationic polymer was synthesized by polyaddition of 4-chloromethyl-1,3-dioxolan-2-one and diethylenetriamine in molten salts. The polyaddition proceeded through nucleophilic addition of the primary amino group to the cyclic carbonate structure and quarternization of the secondary amino group with the chloromethyl group. The resulting cationic polymer was a good and recyclable catalyst for the reaction of carbon dioxide and epoxides owing to the ammonium structure. The complexation with DNA was confirmed by dynamic light scattering and zeta potential measurements, and it suggests the potential application as a carrier for drug delivery system.
- Ochiai, Bungo,Koda, Kazuhiro,Endo, Takeshi
-
experimental part
p. 47 - 51
(2012/04/10)
-
- Converting wastes into added value products: From glycerol to glycerol carbonate, glycidol and epichlorohydrin using environmentally friendly synthetic routes
-
Glycerol carbonate, synthesised via a non-phosgene route using glycerol and CO2 or urea in presence of a heterogeneous catalyst, was efficiently converted into a series of derivatives through the functionalization of the -OH moiety, using high yield, high selectivity synthetic routes not affecting the carbonate functionality. So, for example, glycerol carbonate was converted into epichlorohydrin, a product that has a large industrial application, under very mild conditions, using a two-step reaction with a 98% yield and 100% selectivity. The high yield and mild reaction conditions (very often close to the ambient conditions) make the environmentally friendly synthetic approach described in this work of potential applicative interest. All compounds prepared were fully characterized.
- Dibenedetto, Angela,Angelini, Antonella,Aresta, Michele,Ethiraj, Jayashree,Fragale, Carlo,Nocito, Francesco
-
experimental part
p. 1308 - 1313
(2011/04/12)
-
- Aerobic oxidative carboxylation of olefins with metalloporphyrin catalysts
-
Dioxo(tetraphenylporphyrinato)ruthenium(vi) and quaternary onium salt were successfully developed as catalysts to initiate a three component reaction of olefin, O2, and CO2 at ambient temperature under low pressure. The reaction can be carried out under solvent-free or solvent conditions. Styrene carbonate was obtained in 76% yield with 100% selectivity using 4 mol% of catalyst under optimized conditions.
- Bai, Dongsheng,Jing, Huanwang
-
supporting information; scheme or table
p. 39 - 41
(2010/05/17)
-
- Poly(ethylene glycol): An alternative solvent for the synthesis of cyclic carbonate from vicinal halohydrin and carbon dioxide
-
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
-
experimental part
p. 917 - 920
(2010/02/16)
-
- One-component catalysts for cyclic carbonate synthesis
-
Homogeneous and immobilized one-component catalysts for the conversion of epoxides and carbon dioxide into cyclic carbonates at atmospheric pressure and room temperature have been developed. The Royal Society of Chemistry 2009.
- Melendez, Jaisiel,North, Michael,Villuendas, Pedro
-
supporting information; experimental part
p. 2577 - 2579
(2009/10/17)
-
- Constructing the OCF2O moiety using BrF3
-
(Chemical Equation Presented) A general preparation for aromatic and aliphatic, cyclic as well as linear, symmetric and asymmetric difluoromethylenedioxy derivatives is described. The alcohols were reacted with thiophosgene to give thiocarbonates, which in turn were reacted with BrF 3. The fluorination step is complete in seconds with moderate to high yields under mild conditions.
- Hagooly, Youlia,Rozen, Shlomo
-
p. 6780 - 6783
(2008/12/22)
-
- New Addition Reaction of Active Ester or Cyclic Ester with Epoxy Compounds Catalyzed by Insoluble Polystyrene-bound Quaternary Phosphonium or Ammonium Salts
-
Regioselective addition reaction of active ester S-phenyl thioacetate with 2-phenoxymethyloxirane was catalyzed by insoluble polystyrene-bound quaternary phosphonium or ammonium salts and gave 1-phenoxy-3-thiophenoxy-2-propyl acetate.Five-membered cyclic carbonates were also synthesized by the reaction of cyclic ester β-butyrolactone with some epoxy compounds using the same polymeric catalysts.
- Nishikubo, Tadatomi,Shiina, Atsushi,Isobe, Naoki
-
p. 1605 - 1608
(2007/10/02)
-
- CONVENIENT SYNTHESES OF CYCLIC CARBONATES BY NEW REACTION OF OXIRANES WITH β-BUTYROLACTONE
-
Cyclic carbonates were synthesized by reactions of the corresponding oxiranes with β-butyrolactone using quaternary salts such as tetrabutylammonium bromide or 18-crown-6=KBr as catalyst.
- Nishikubo, Tadatomi,Iizawa, Takashi,Iida, Makoto,Isobe, Naoki
-
p. 3741 - 3744
(2007/10/02)
-
