- Synthesis of Poly- And the First Perfluoroalkyl-N(SO2F)2 Derivatives: Improved Methods for the Preparation of XN(SO2F)2 (X = H, Cl) and Single-Crystal Diffraction Studies of HN(SO2Cl)2, HN(SO2F)2, and CF3CH2N(SO2F)2
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The preparation of HN(SO2F)2 was achieved conveniently by fluorination of HN(SO2C1)2 with SbF3. Reactions of Hg[N(SO2F)2]2 with fluoroalkyl iodides RI (R = i-C3F7CH2CH2 and CF3CH2) gave i-C3F7CH2CH2N(SO2F) 2 (1) and CF3CH2N(SO2F)2 (2). The chlorination of Hg[N(SO2F)2]2 provided a high-yield method of synthesizing the well-known ClN(SO2F)2. N-alkylation of ClN(SO2F)2 with fluorinated ethenes CF2=CHal2 (CHal2 = CF2, CFCl, and CCl2) resulted in the formation of CF2ClCF2N(SO2F)2 (3), CF2ClCFClN(SO2F)2 (4a, major), CFCl2-CF2N(SO2F)2 (4b, minor), and CCl3CF2N(SO2F)2 (5). The synthesis of the first perfluoroalkyl-N(SO2F)2 derivatives CF3N(SO2F)2 (6), C2F5N(SO2F)2 (7), n-C3F7N(SO2F)2 (8), and n-C4F9N(SO2F)2 (9) was accomplished with moderate-to-good yields by reacting ClN(SO2F)2 with iodoperfluoroalkanes RFI (RF = CF3, C2F5, n-C3F7, and n-C4F9). Similarly, ClN(SO2F)2 reacted with CF3CH2I to give 2. Photolysis of ClN(SO2F)2 with iodoperfluoroalkanes RFI (RF = n-C3F7, and n-C4F9) gave 8 and 9 in low yields. HN(SO2F)2 belongs to a monoclinic crystal system P21 (No. 4): a = 5.1619(5) ?, b = 7.8153(8) ?, c = 6.8028(7) ?, β = 100.411(2)°, V= 269.92(5) ?3, Z= 2. HN(SO2Cl)2 is monoclinic P21/c (No. 14): a = 7.7331(3) ?, b = 10.0542(2) ?, c = 9.3197(3) ?, β = 109.495(1)°, V = 683.07(4) ?3, Z= 4. CF3CH2N(SO2F)2 is orthorhombic P212121 (No. 19): a= 11.1245(1) ?, b = 28.8003(4) ?, c = 7.7120 ?, V = 2470.90(4) ?3, Z = 12.
- Krumm, Burkhard,Vij, Ashwani,Kirchmeier, Robert L.,JeaN'Ne,Shreeve
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- Molecular dynamics simulation and pulsed-field gradient NMR studies of Bis(fluorosulfonyl)imide (FSI) and Bis[(trifluoromethyl)sulfonyl]imide (TFSI)-based ionic liquids
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The pulsed-field-gradient spin-echo NMR measurements have been performed on 1-ethyl-3-methylimidazolium bis(fluorosulfonyl)imide ([emim][FSI]) and 1-ethyl-3-methylimidazolium [bis[(trifluoromethyl)sulfonyl]imide] ([emim][TFSI]) over a wide temperature range from 233 to 400 K. Molecular dynamics (MD) simulations have been performed on [emim][FSI], [emim][TFSI], [N-methyl-N-propylpyrrolidinium][FSI] ([pyr13][FSI]), and [pyr 13][TFSI] utilizing a many-body polarizable force field. An excellent agreement between the ion self-diffusion coefficients from MD simulations and pfg-NMR experiments has been observed for [emim][FSI] and [emim][TFSI] ILs. The structure factor of [pyr13][FSI], [pyr14][TFSI], and [emim][TFSI] agreed well with the previously reported X-ray diffraction data performed by Umebayashi group. Ion packing in the liquid state is compared with packing in the corresponding ionic crystal. Faster transport found in the FSI-based ILs compared to that in TFSI-based ILs is associated with the smaller size of FSI- anion and lower cation-anion binding energies. A significant artificial increase of the barriers (by 3 kcal/mol) for the FSI - anion conformational transitions did not result in slowing down of ion transport, indicating that the ion dynamics is insensitive to the FSI - anion torsional energetic, while the same increase of the TFSI - anion barriers in [emim][TFSI] and [pyr13][TFSI] ILs resulted in slowing down of the cation and anion transport by 40-50%. Details of ion rotational and translational motion, coupling of the rotational and translational relaxation are also discussed. ? 2010 American Chemical Society.
- Borodin, Oleg,Gorecki,Smith, Grant D.,Armand, Michel
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- New inorganic ionic liquids possessing low melting temperatures and wide electrochemical windows: Ternary mixtures of alkali bis(fluorosulfonyl)amides
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Four kinds of ternary phase diagrams of alkali bis(fluorosulfonyl)amides, LiFSA-NaFSA-KFSA, LiFSA-NaFSA-CsFSA, LiFSA-KFSA-CsFSA and NaFSA-KFSA-CsFSA, have been constructed. All the ternary systems possess the only one eutectic point around equimolar compo
- Kubota, Keigo,Nohira, Toshiyuki,Hagiwara, Rika
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- METHOD FOR PREPARING HYDROGEN BIS(FLUOROSULFONYL)IMIDE AND METHOD FOR PREPARING LITHIUM BIS(FLUOROSULFONYL)IMIDE
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A method for preparing hydrogen bis(fluorosulfonyl)imide including contacting sulfonyl fluoride with hexamethyl disilazane in an organic solvent. The disclosure also provides a method for preparing lithium bis(fluorosulfonyl)imide (LiFSI). The method includes contacting sulfonyl fluoride with hexamethyl disilazane in an organic solvent and yielding hydrogen bis(fluorosulfonyl)imide; and contacting hydrogen bis(fluorosulfonyl)imide with a lithium compound and yielding lithium bis(fluorosulfonyl)imide.
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Paragraph 0052-0053
(2020/06/07)
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- A bifluoride sulfonyl imide lithium salt preparation method
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The invention relates to an imidodisulfuryl fluoride lithium salt preparation method. The method includes steps: (1) fluoridation, to be more specific, adopting imidodisulfuryl chloride and hydrogen fluoride for synthesis of intermediate imidodisulfuryl fluoride under the action of catalysts; (2) subjecting imidodisulfuryl fluoride obtained at the step (1) to reaction with lithium carboxylate to obtain imidodisulfuryl fluoride lithium salt. The method is low in cost, low in by-product quantity and simple in aftertreatment, product quality and purity are guaranteed, and metal ion control is guaranteed especially. Therefore, the preparation method through which high-quality high-purity products can be obtained is economical and suitable for industrial production.
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Paragraph 0046-0049
(2019/03/06)
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- Method for efficiently preparing sulfuryl fluorides compound by catalytic fluorination
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The invention belongs to the technical field of the chemical synthesis, and particularly relates to a method for efficiently preparing a sulfuryl fluorides compound by catalytic fluorination. The provided method for efficiently preparing the sulfuryl fluorides compound by the catalytic fluorination comprises the following steps: enabling a sulfonyl chlorides compound to react with a hydroge fluoride under the action of a catalyst of a sulfonic acids derivative, to obtain the sulfuryl fluorides compound. A novel catalytic technology is provided, and the method has extensive substrate applicability. Efficient catalytic efficiency and yield are expressed.
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Paragraph 0087; 0088; 0089; 0090; 0091; 0092
(2019/05/22)
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- PROCESS FOR PREPARING BIS (FLUOROSULFONYL) IMIDE ACID AND SALTS THEREOF
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A process for preparing bis(fluorosulfonyl)imide acid, comprising the reaction of sulfamic acid or a salt thereof with a halosulfuric acid and at least one fluorinating agent selected from SOF2, F-SO2-F and SF4, then the recovery of the bis(fluorosulfonyl)imide acid, is described. Also described is a process for preparing bis(fluorosulfonyl)imide salts from the bis(fluorosulfonyl)imide acid thus prepared.
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Page/Page column 10
(2019/05/10)
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- SALTS FOR MULTIVALENT ION BATTERIES
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Methods for preparing electrolyte salts for alkaline earth metal-ion batteries (e.g., calcium and magnesium ion batteries) are described. The electrolyte salts comprise alkaline earth metal (e.g., Mg or Ca) salts of bis(fluorosulfonyl)imide (FSI) and 3,4-dicyano-2-trifluoromethylimidazole (TDI). The methods comprise contacting FSI or TDI with an alkaline earth metal bis(trifluoroacetate) salt in trifluoroacetic acid.
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Paragraph 0029; 0030
(2017/07/14)
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- METHOD FOR PREPARATION OF BIS(FLUOROSULFONYL)-IMIDE
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The invention relates to a method for the preparation of bis(fluorosulfonyl)-imide and its derivatives at elevated temperature.
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Page/Page column 26; 27
(2016/11/21)
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- Method for producing bis(fluorosulfonyl)imide salt, method for producing fluorosulfate, and method for producing bis(fluorosulfonyl)imide onium salt
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According to the method for producing bis(fluorosulfonyl)imide salt of the present invention, the method for producing fluorosulfate, and the method for producing bis(fluorosulfonyl)imide onium salt, first, an aqueous solution is prepared by dissolving a mixed liquid containing bis(fluorosulfonyl)imide and fluorosulfonic acid in water. Then, the aqueous solution is neutralized with an alkaline compound, producing bis(fluorosulfonyl)imide salt and fluorosulfate. In the methods, bis(fluorosulfonyl)imide salt, fluorosulfate, and bis(fluorosulfonyl)imide onium salt can be obtained safely and easily.
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Page/Page column 11
(2015/11/09)
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- Synthesis of bis(fluorosulfonyl)imide
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The present invention provides methods for producing bis(fluorosulfonyl) compounds of the formula: [in-line-formulae]F—S(O)2—Z—S(O)2—F??I[/in-line-formulae] by contacting a nonfluorohalide compound of the formula: [in-line-formulae]X—S(O)2—Z—S(O)2—X[/in-line-formulae] with bismuth trifluoride under conditions sufficient to produce the bis(fluorosulfonyl) compound of Formula I, where Z and X are those defined herein.
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Page/Page column 8; 9
(2013/03/26)
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- SYNTHESIS OF TETRABUTYLAMMONIUM BIS(FLUOROSULFONYL)IMIDE AND RELATED SALTS
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The present invention is directed to methods comprising adding ammonia to a sulfuryl fluoride solution to form the anion of bis(fluorosulfonyl)amine under conditions well suited for large-scale production. The bis(fluorosulfonyl)amine so produced can be isolated by methods described in the prior art, or isolated as an organic ion pair, such as an alkylammonium solid salt, or as an ionic liquid.
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Page/Page column 5
(2012/10/08)
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- FLUOROSULFONYL IMIDE SALT AND METHOD FOR PRODUCING FLUOROSULFONYL IMIDE SALT
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The present invention provides a method for producing a fluorisulfonylimide salt, which enables reducing the impurity content and continuous operation for a long time, and a fluorosulfonyl imide salt. The fluorosulfonyl imide salt of the present invention has a K content of 10,000 ppm or less. The method for producing a fluorosulfonyl imide salt of the present invention is that after a fluorination reaction of chlorosulfonyl imde or a salt thereof, the reaction solution is brought into contact with an aqueous alkaline solution so as to remove impurities. The fluorosulfonyl imide salt of the present invention, in which various impirities are reduced to extremely low levels, is useful as an electrolyte used in a lithium secondary battery, a capacitor or the like, an ionic liquid, or an intermediate for a sulfonyl imide salt, and the like. It is expected that use of the fluorosulfonyl imide salt of the present invention as an electrolyte leads to a high-performance electrochemical device.
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Page/Page column 11
(2012/03/08)
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- SULFONYLIMIDE SALT AND METHOD FOR PRODUCING THE SAME
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The present invention provides a method for producing fluorosulfonylimides more safely, rapidly and efficiently, which enables suppression of production of by-products, and fluorosulfonylimides. The method for producing a fluorosulfonylimide salt of the present invention includes a step of reacting a fluoride compound containing at least one element selected from the group consisting of elements of Group 11 to Group 15 and Period 4 to Period 6 (excluding arsenic and antimony) with a compound represented by the following general formula (I) to give a fluorosulfonylimide salt represented by the general formula (II): wherein R1 denotes at least one element selected from the group consisting of elements of Group 11 to Group 15 and Period 4 to Period 6 (excluding arsenic and antimony); R3 denotes fluorine, chlorine or a fluorinated alkyl group having 1 to 6 carbon atoms; R4 denotes fluorine or a fluorinated alkyl group having 1 to 6 carbon atoms; and m denotes an integer of 2 or 3.
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Page/Page column 11
(2011/02/26)
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- Sulphonyl-1,2,4-triazole salts
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The invention relates to triazole salts, to their preparation and to applications thereof. The salts have at least one anionic triazolium group which carries at least one chlorosulphonyl, fluorosulphonyl or alkoxyfluorosulphonyl group, each of the anionic groups being combined with a proton or a cation that has a valency of less than or equal to 4. The salts are useful as synthesis reagents, as chemical-reaction or polymerization catalysts, and as ion-conducting materials for electrochemical generators, supercapacitors and electrochromic devices.
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Page/Page column 36
(2011/04/24)
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- A new method of the preparation of imido-bis(sulfuric acid) dihalogenide, (F,Cl), and the potassium salt of imido-bis(sulfuric acid) difluoride
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The article describes a new and effective synthesis of pure imido-bis(sulfuric acid) dihalogenides (halogenide = F, Cl) and the potassium salt of imido-bis(sulfuric acid) difluoride, KN(SO2F)2.
- Beran, Martin,Prihoda, Jiri
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