- Recyclable polymer-supported iodobenzene-mediated electrocatalytic fluorination in ionic liquid
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The electrochemical fluorination of organosulfur compounds in triethylamine/hydrofluoric acid (Et3N-5HF) with polystyrene-supported iodobenzene (PSIB) and tetraethylammonium chloride (Et4NCl) was performed successfully in an undivided cell under constant current conditions to afford the corresponding fluorinated compounds in moderate to good yields. Recycle use of the PSIB could be achieved due to its easy separation. Notably, the mediatory activity of the iodobenzene derivative was not appreciably changed even after 10 recycle uses.
- Sawamura, Takahiro,Kuribayashi, Shunsuke,Inagi, Shinsuke,Fuchigami, Toshio
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Read Online
- Highly selective anodic monofluorination of 4-arylthio-1,3-dioxolan-2-ones: A marked solvent effect on product selectivity
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This is the first example of a solvent effect on fluorinated product selectivity; anodic fluorination of 4-arylthio-1,3-dioxolan-2-ones in CH2Cl2 containing a fluoride supporting electrolyte using an undivided cell provided the fluoro-desulfurization product, 4-fluoro-1,3-dioxolan-2-one preferentially while anodic fluorination in DME resulted in α-fluorination, without desulfurization, selectively.
- Ishii,Yamada,Fuchigami
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Read Online
- Electroorganic synthesis under solvent-free conditions. Highly regioselective anodic monofluorination of cyclic ethers, lactones, and a cyclic carbonate
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Regioselective anodic fluorination of cyclic ethers, lactones, and a cyclic carbonate in Et4NF·nHF (n = 4, 5) and Et3N·5HF without a solvent was successfully carried out to give the corresponding monofluorinated products in moderate yields. This is the first report of direct electrochemical fluorination of cyclic ethers, lactones, and a cyclic carbonate using anodic fluorination.
- Hasegawa, Masaru,Ishii, Hideki,Fuchigami, Toshio
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Read Online
- Highly Robust {Ln4}-Organic Frameworks (Ln = Ho, Yb) for Excellent Catalytic Performance on Cycloaddition Reaction of Epoxides with CO2 and Knoevenagel Condensation
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Due to the high electron charge, large ion radius, and plentiful outer hybrid orbitals of LnIII cations, microporous Ln-MOFs can be used as Lewis acidic catalysts with high catalytic activity for a variety of organic reactions, which prompts us to explore cluster-based nanoporous Ln-MOFs by employing structure-oriented ligands. Herein, the exquisite combination of coplanar [Ln4(μ3–OH)2(μ2–HCO2)(H2O)2] clusters (abbreviated as {Ln4}) and the structure-oriented multifunctional ligand of 2,6-bis(2,4- dicarboxylphenyl)-4-(4-carboxylphenyl)pyridine (H5BDCP) led to two isomorphic nanoporous frameworks of {(Me2NH2)[Yb4(BDCP)2(μ3–OH)2(μ2–HCO2)(H2O)2]·5DMF·H2O}n (NUC-38Yb) and {(Me2NH2)[Ho4(BDCP)2(μ3–OH)2(μ2– HCO2)(H2O)2]·6DMF·3H2O}n (NUC-38Ho). To the best of our knowledge, NUC-38Ho and NUC-38Yb are rarely reported {Ln4}-based three-dimensional (3D) frameworks with embedded hierarchical triangular-microporous and hexagonal-nanoporous channels, which are shaped by six rows of coplanar {Ln4} clusters and characterized by plentiful coexisting Lewis acid–base sites on the inner wall including open LnIII sites, Npyridine atoms, μ3–OH, and μ2–HCO2. Catalytic experiments performed using NUC-38Yb as the representative exhibited that NUC-38Yb possessed a high catalytic activity on the cycloaddition reactions of epoxides with CO2 under mild conditions, which can be ascribed to its structural advantages including nanoscale channels, rich bifunctional active sites, large surface areas, and chemical stability. Moreover, NUC-38Yb, as a heterogeneous catalyst, could greatly accelerate the Knoevenagel condensation reactions of aldehydes and malononitrile. Hence, this work paves the way for the construction of functional Ln-cluster-based nanoporous metal–organic frameworks (MOFs) by elaborately designing functional ligands with transnormal connection modes.
- Chen, Hongtai,Li, Qiaoling,Liu, Shurong,Lv, Hongxiao,Zhang, Tao,Zhang, Xiutang
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p. 14916 - 14925
(2021/12/09)
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- Rapid continuous flow synthesis process of fluoroethylene carbonate
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The invention discloses a rapid continuous flow synthesis process of fluoroethylene carbonate, which comprises the following steps. Step I, EC vent nitrogen is added to the reaction kettle to be heated to the reaction temperature, thionyl chloride is added dropwise, and then an amount of AIBN is dropwise added, and the reaction 1.5 - 2h is carried out under 200 - 220Pa under reduced pressure. Step II. When the whole reaction of chloroethylene carbonate is completed, the reaction process is monitored by gas chromatography, and the reaction progress is monitored 1 - 3h through gas chromatography, and then the reaction process is monitored by gas chromatography, and the filtrate is filtered and the filtrate is filtered and the filtrate is 30 °C evaporated off under reduced pressure. The method avoids tedious work of repeated long-time operation in the past process, reduces labor intensity, shortens reaction time, and is suitable for continuous industrial production.
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Paragraph 0022-0027
(2021/11/10)
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- Preparation method of fluoroethylene carbonate
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The invention discloses a preparation method of fluoroethylene carbonate. The preparation method comprises the steps of preparation of phenyl iodine difluoride and preparation of fluoroethylene carbonate. The method has the beneficial effects that the synthesis of the fluoroethylene carbonate does not need to use a toxic chlorination reagent, and the cheap raw materials hydrogen peroxide and hydrogen fluoride are used; according to the preparation method, the high-purity fluoroethylene carbonate is obtained by directly distilling in a fluoroethylene carbonate synthesis reaction kettle, and the operation is simple; wherein, the acetic acid, iodobenzene, the organic solvent and the catalyst palladium acetate (II) in the preparation process of fluoroethylene carbonate are recycled, so that the cost is saved.
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Paragraph 0026; 0029-0031; 0034-0036; 0039-0041; ...
(2021/07/21)
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- Fluoroethylene carbonate production method
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The invention relates to a fluoroethylene carbonate production method. A purpose of the invention is mainly to solve the problems of high catalyst cost and low product yield in the prior art. According to the technical scheme of the invention, the method comprises: adding chloroethylene carbonate into a reactor, adding a polar aprotic solvent, a catalyst and a fluorinating reagent, reacting undera certain reaction condition, and separating reaction liquid by using a separation unit after the reaction is finished so as to obtain the fluoroethylene carbonate product. With the technical scheme of the invention, the problems in the prior art are well solved. The method of the invention can be applied to production of fluoroethylene carbonate.
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Paragraph 0020-0047
(2020/03/09)
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- Process for fluorinating inorganic or organic compounds by direct fluorination
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The invention relates to the use of a fluorinated gas, wherein the elemental fluorine (F2) is present at a high concentration, the present invention relates to a process for producing fluorinated compounds by direct fluorination using a fluorination gas in which elemental fluorine (F2) is present at a high concentration, such as a concentration of elemental fluorine (F2), in particular equal to much higher than 15 vol% or even 20 vol% (i.e., at least 15 vol% or even 20 vol%), and to a process for producing fluorinated compounds by direct fluorination using a fluorination gas. The process of the present invention relates to the manufacture of fluorinated compounds other than fluorinated benzene by direct fluorination, in particular to the preparation of fluorinated organic compounds, end products and intermediates for use in agricultural, pharmaceutical, electronic, catalyst, solvent and other functional chemical applications. The fluorination process of the invention can be carried outin batches or in a continuous manner. If the process of the invention is carried out in batches, a column (tower) reactor may be used. If the process of the invention is continuous, a microreactor may be used.
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Paragraph 00273-00274; 0283-0286
(2020/07/14)
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- Preparation method of fluoroethylene carbonate
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The invention relates to a direct fluorination synthesis method of fluoroethylene carbonate, which includes steps of performing direct fluorination to ethylene carbonate and a fluorination reagent inthe presence/absence of a solvent and in the absence of a catalyst to prepare the fluoroethylene carbonate, performing fluorination regeneration to a product of the fluorination reagent after reaction, thus recycling the fluorination reagent for the direct fluorination of the ethylene carbonate. Being different from indirect fluorination, the method can efficiently produce the fluoroethylene carbonate through a direct one-step reaction, thus reducing reaction process. The product can reach high level in purity, chromaticity and yield of the product. The method is suitable for large-scale production.
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Paragraph 0020; 0024; 0025
(2018/06/15)
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- Method for preparing fluoroethylene carbonate by direct fluorination
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The invention relates to a method for preparing fluoroethylene carbonate by direct fluorination. The method comprises the following steps: carrying out a reaction on fluorine gas with a fluorinating agent precursor to prepare a fluorinating agent, and directly fluorinating ethylene carbonate with the prepared fluorinating agent under a condition with a solvent or without a solvent, and without a catalyst to prepare the fluoroethylene carbonate, wherein a product obtained after the reaction of the fluorinating agent is subjected to fluorinating regeneration, and is recycled for a fluorination reaction of ethylene carbonate. According to the method provided by the invention, the problem of excessive fluorine gas activity is overcome, the fluorine gas is indirectly converted into the mild andefficient fluorinating reagent, the utilization rate and the safety of the fluorine gas are improved, and the environmental pollution is reduced.
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Paragraph 0021-0023; 0025; 0027-0029
(2018/07/28)
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- A synthetic fluorocholine of vinyl carbonate fluosilicic acid production process
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The invention discloses a technology for synthesizing fluoroethylene carbonate with fluosilicic acid. The technology comprises the steps of heating up the ethylene carbonate to 48-52DEG C, adding fluosilicic acid to obtain mixed liquor I, heating up the mixed liquor to 55-70DEG C, keeping at constant temperature, dripping a phase shift catalyst, then dripping an amine catalyst to obtain mixed liquor II, filtering impurities in the mixed liquor II, heating up the filtrate to 60-75DEG C, reacting at constant temperature, cooling, dehydrating and filtering impurities, and collecting the reaction liquid through distillation, so as to obtain the finished product- fluoroethylene carbonate. The technology has the advantages of simple steps, easy operation, small investment in production equipment and the like, fluorine waste gas which is generated in production of a phosphatic fertilizer in a phosphate fertilizer plant and cannot be exhausted is taken as the raw material, and the resources are rich and low in cost, so that the environmental protection problem in production of the phosphatic fertilizer is solved, the waste gas is recycled, the technology gets a double advantage, and has very good social benefit and economic benefit.
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Paragraph 0036-0041
(2017/03/14)
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- Electrochemical fluorination using halogen mediators in ionic liquid hydrogen fluoride salt
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In order to utilize ammomium halides (Et4NX, X=Cl, Br, I) as halogenmediator for electrocatalytic fluorination, cyclic voltammetry measurements of the halides were investigated. The catalytic current of the halides in the presence of a dithioacatal compound was observed and the macro-scale electrolysis of dithioacetals using the halogen mediator was also carried out in ionic liquid hydrogen fluoride (HF) salt to give the corresponding fluorinated products in excellent yields. The recycle use of the halogen mediator in the electrochemical fluorination was successfully demonstrated. More inexpensive halides such as potassium bromide and potassium iodide could be soluble in HF salt and worked well as halogen mediator for the electrocatalytic fluorination.
- Takahashi, Kohta,Inagi, Shinsuke,Fuchigami, Toshio
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p. G3046-G3052
(2013/07/05)
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- MANUFACTURE OF DIFLUOROETHYLENE CARBONATE, TRIFLUOROETHYLENE CARBONATE AND TETRAFLUOROETHYLENE CARBONATE
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Difluoroethylene carbonate, trifluoroethylene and tetrafluoroethylene carbonate are produced by the reaction between elemental fluorine and ethylene carbonate or fluorinated ethylene carbonates with a lower degree of fluorination.
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Page/Page column 11-13
(2011/04/24)
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- CONTINUOUS PREPARATION OF CARBONATES
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A process for the manufacture of fluoroethylene carbonate, difluoroethylene carbonate, fluoromethyl methyl carbonate and difluorinated dimethyl carbonate from ethylene carbonate and dimethyl carbonate and F2 is described wherein the fluorination process is performed continuously.
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Page/Page column 10-11
(2011/04/24)
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- PROCESS FOR PREPARING FLUORINATED 1,3-DIOXOLAN 2-ONE
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The present invention provides a process for preparing fluorinated 1,3-dioxolan-2-one by reacting a derivative of 1,3-dioxolan-2-one having halogen atom other than fluorine with an amine hydrofluoride in an organic solvent, and in this preparation process, fluorinated 1,3-dioxolane-2-on can be prepared in a short period of time by liquid-liquid reaction while maintaining high yield, by using a derivative of 1,3-dioxolan-2-one having halogen atom other than fluorine as a starting material and fluorinating the derivative with a fluorinating agent.
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Page/Page column 9-10
(2011/02/15)
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- Container containing fluorinated organic carbonates
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The invention provides a container containing a fluorinated organic carbonate and a gas atmosphere which contains argon, xenon or a mixture of both. Fluorinated organic carbonates are highly suitable as solvents or additives for solvent in Li ion batteries and consequently, must be kept in a very pure state even during expanded times of storage. The argon or xenon gas atmosphere prevents the intrusion of air or moisture even if the container is opened and the liquid handled in an environment of common air. The invention also provides for a method of storing fluorinated organic carbonates in a safe manner.
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Page/Page column 4
(2010/07/03)
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- Manufacturing method and apparatus of 4-fluoroethylene carbonate control system of autonomous intelligent distributed control modules
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Disclosed herein is a method of producing 4-fluoroethylene carbonate, in which ethylene carbonate reacts with a mixture of fluorine and nitrogen gases. The method comprises feeding a mixture gas of fluorine gas and nitrogen gas into a reactor having ethylene carbonate charged therein, so as to react the ethylene carbonate with the mixture gas of the fluorine gas and the nitrogen gas. The mixture gas fed in the reactor is regulated to have a desired bubble size while passing through a gas bubble regulating column, in which a packing for a packed column is packed. In the method, EC directly reacts with F2/N2 mixture gas to produce FEC, thus a purification process is simple and it is possible to produce FEC at high conversion efficiency and selectivity.
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Page/Page column 3-5
(2008/06/13)
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- METHOD FOR PRODUCING 4-FLUORO-1,3-DIOXOLAN-2-ONE
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The invention relates to a method for producing 4-fluoro-1,3-dioxolan-2-one. According to the invention, ethylene carbonate is reacted with 3 to 20 % by weight of 4-fluoro-1,3-dioxolan-2-one (with regard to ethylene carbonate) serving as a solvent for ethylene carbonate, and fluorine or a mixture containing the fluorine in an inert gas is introduced into this solution at a temperature ranging from 15 to 45 °C.
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Page/Page column 3; 4
(2008/06/13)
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- Development of direct fluorination technology for application to materials for lithium battery
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Direct fluorination of 1,3-dioxolan-2-one with elemental fluorine was successfully carried out to provide 4-fluoro-1,3-dioxolan-2-one, which was expected as an additive for lithium ion secondary battery. 4-Fluoro-1,3-dioxolan-2-one was also further fluorinated with elemental fluorine to give three isomers of difluoro derivatives by the same methodology. Another topic is the preparation of trifluoromethanesulfonyl fluoride, an intermediate of lithium battery electrolyte, by the reaction of methanesulfonyl fluoride with elemental fluorine. The use of perfluoro-2-methylpentane as a solvent gave satisfactory selectivity of trifluoromethanesulfonyl fluoride.
- Kobayashi, Masafumi,Inoguchi, Tetsuya,Iida, Takashi,Tanioka, Takashi,Kumase, Hiroshi,Fukai, Yasushi
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p. 105 - 110
(2007/10/03)
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- Electrolytic partial fluorination of organic compound. Part: 53 Highly regioselective anodic mono- and difluorination of 4-arylthio-1,3-dioxolan-2-ones. A marked solvent effect on fluorinated product selectivity
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Anodic fluorination of 4-arylthio-1,3-dioxolan-2-ones was investigated using various supporting fluoride salts and solvents. Their fluoro-desulfurization took place predominantly in Et4NF·5HF/CH2Cl2 while the use of Et4NF·4HF/DME resulted in α-fluorination, without the desulfurization, selectively. Electrolytic solvents affected markedly the product selectivity as compared with supporting fluoride salts. This is the first example of a solvent effect on the fluorinated product selectivity in the anodic fluorination.
- Ishii, Hideki,Yamada, Norihisa,Fuchigami, Toshio
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p. 9067 - 9072
(2007/10/03)
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