CN112552213A - Preparation method of high-purity alkylsulfonylfluoroaniline salt - Google Patents
Preparation method of high-purity alkylsulfonylfluoroaniline salt Download PDFInfo
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- CN112552213A CN112552213A CN202011552277.7A CN202011552277A CN112552213A CN 112552213 A CN112552213 A CN 112552213A CN 202011552277 A CN202011552277 A CN 202011552277A CN 112552213 A CN112552213 A CN 112552213A
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- 150000003839 salts Chemical class 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims description 7
- 239000011259 mixed solution Substances 0.000 claims abstract description 96
- -1 alkylsulfonyl chloride Chemical compound 0.000 claims abstract description 29
- 238000003756 stirring Methods 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 239000003960 organic solvent Substances 0.000 claims abstract description 16
- 125000004390 alkyl sulfonyl group Chemical group 0.000 claims abstract description 15
- MGNPLIACIXIYJE-UHFFFAOYSA-N n-fluoroaniline Chemical compound FNC1=CC=CC=C1 MGNPLIACIXIYJE-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 7
- 239000011230 binding agent Substances 0.000 claims abstract description 7
- 150000002148 esters Chemical class 0.000 claims abstract description 7
- 239000012535 impurity Substances 0.000 claims abstract description 5
- 239000000047 product Substances 0.000 claims abstract description 5
- 239000012043 crude product Substances 0.000 claims abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 51
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 18
- 238000001914 filtration Methods 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 238000000926 separation method Methods 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 12
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 10
- 238000004821 distillation Methods 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 6
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-diisopropylethylamine Substances CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 6
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- 125000001153 fluoro group Chemical group F* 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 3
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
- 150000001768 cations Chemical group 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims 1
- 239000011737 fluorine Substances 0.000 claims 1
- 230000007613 environmental effect Effects 0.000 abstract 1
- 150000002500 ions Chemical class 0.000 abstract 1
- 239000007787 solid Substances 0.000 description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 18
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 18
- 239000000706 filtrate Substances 0.000 description 18
- GRGCWBWNLSTIEN-UHFFFAOYSA-N trifluoromethanesulfonyl chloride Chemical compound FC(F)(F)S(Cl)(=O)=O GRGCWBWNLSTIEN-UHFFFAOYSA-N 0.000 description 17
- 239000002994 raw material Substances 0.000 description 10
- 238000004255 ion exchange chromatography Methods 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 239000000376 reactant Substances 0.000 description 9
- 238000010992 reflux Methods 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- CXCHEKCRJQRVNG-UHFFFAOYSA-N 2,2,2-trifluoroethanesulfonyl chloride Chemical compound FC(F)(F)CS(Cl)(=O)=O CXCHEKCRJQRVNG-UHFFFAOYSA-N 0.000 description 7
- NOXLGCOSAFGMDV-UHFFFAOYSA-N 2,3,4,5,6-pentafluoroaniline Chemical compound NC1=C(F)C(F)=C(F)C(F)=C1F NOXLGCOSAFGMDV-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- VQHMMOSXFHZLPI-UHFFFAOYSA-N 1,1,2,2,2-pentafluoroethanesulfonyl chloride Chemical compound FC(F)(F)C(F)(F)S(Cl)(=O)=O VQHMMOSXFHZLPI-UHFFFAOYSA-N 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- BEECAQIHCYTZHC-UHFFFAOYSA-N 2,3,4,5-tetrafluoroaniline Chemical compound NC1=CC(F)=C(F)C(F)=C1F BEECAQIHCYTZHC-UHFFFAOYSA-N 0.000 description 2
- ODUZJBKKYBQIBX-UHFFFAOYSA-N 2,6-difluoroaniline Chemical compound NC1=C(F)C=CC=C1F ODUZJBKKYBQIBX-UHFFFAOYSA-N 0.000 description 2
- OXKHPRFGCFJUSK-UHFFFAOYSA-N 3,3,3-trifluoropropane-1-sulfonyl chloride Chemical compound FC(F)(F)CCS(Cl)(=O)=O OXKHPRFGCFJUSK-UHFFFAOYSA-N 0.000 description 2
- SZRDJHHKIJHJHQ-UHFFFAOYSA-N 3,4,5-trifluoroaniline Chemical compound NC1=CC(F)=C(F)C(F)=C1 SZRDJHHKIJHJHQ-UHFFFAOYSA-N 0.000 description 2
- AXNUZKSSQHTNPZ-UHFFFAOYSA-N 3,4-difluoroaniline Chemical compound NC1=CC=C(F)C(F)=C1 AXNUZKSSQHTNPZ-UHFFFAOYSA-N 0.000 description 2
- KQOIBXZRCYFZSO-UHFFFAOYSA-N 3,5-difluoroaniline Chemical compound NC1=CC(F)=CC(F)=C1 KQOIBXZRCYFZSO-UHFFFAOYSA-N 0.000 description 2
- QZVQQUVWFIZUBQ-UHFFFAOYSA-N 3-fluoroaniline Chemical compound NC1=CC=CC(F)=C1 QZVQQUVWFIZUBQ-UHFFFAOYSA-N 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- DGHOARDRAMFOLB-UHFFFAOYSA-N C(O)(O)=O.C(Cl)(Cl)(Cl)Cl Chemical compound C(O)(O)=O.C(Cl)(Cl)(Cl)Cl DGHOARDRAMFOLB-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/36—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids
- C07C303/38—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids by reaction of ammonia or amines with sulfonic acids, or with esters, anhydrides, or halides thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing high-purity alkylsulfonylfluoroanilide salt. Mixing fluoroaniline and an acid-binding agent in an organic solvent to prepare a mixed solution I, mixing alkylsulfonyl chloride and the organic solvent to prepare a mixed solution II, dropwise adding the mixed solution I into the mixed solution II under the condition of stirring, and after the reaction is finished, purifying to obtain alkylsulfonylfluoroaniline ester; dissolving the alkyl sulfonyl fluoroaniline ester in an organic solvent to form a mixed solution III, mixing inorganic or organic salt of a target salt to be prepared with the organic solvent to form a mixed solution IV, dropwise adding the mixed solution III into the mixed solution IV while stirring, reacting to obtain an alkyl sulfonyl fluoroaniline salt crude product, and removing impurities and purifying to obtain the high-purity alkyl sulfonyl fluoroaniline salt. The method has the advantages of simple process, high yield, good product quality, environmental protection, high product purity and less impurity ions.
Description
Technical Field
The invention belongs to the field of raw material manufacturing, and particularly relates to a preparation method of high-purity alkylsulfonylfluoroaniline salt.
Background
The invention provides a method for preparing high-purity alkylsulfonylfluoroaniline salt, and a preparation method of the salt is only reported at present. The application cases of the alkyl sulfonyl fluoroaniline salt are still few, and application scenes are yet to be developed. The lithium salt of the alkylsulfonylfluoroaniline can be used as an additive of the lithium ion battery, and has obvious improvement effect on the performance of the battery.
Disclosure of Invention
The invention provides a preparation method of high-purity alkylsulfonylfluoroaniline salt.
The technical scheme adopted by the invention is as follows: a preparation method of high-purity alkylsulfonylfluoroaniline salt comprises the steps of mixing fluoroaniline and an acid-binding agent in an organic solvent to prepare a mixed solution I, mixing alkylsulfonyl chloride and the organic solvent to prepare a mixed solution II, dropwise adding the mixed solution I into the mixed solution II under the condition of stirring, and after the reaction is finished, purifying to obtain alkylsulfonylfluoroaniline ester; dissolving the alkyl sulfonyl fluoroaniline ester in an organic solvent to form a mixed solution III, mixing inorganic or organic salt of a target salt to be prepared with the organic solvent to form a mixed solution IV, dropwise adding the mixed solution III into the mixed solution IV while stirring, reacting to obtain an alkyl sulfonyl fluoroaniline salt crude product, and removing impurities and purifying to obtain the high-purity alkyl sulfonyl fluoroaniline salt.
As a preferred embodiment of the present invention, the chemical structure of said alkyl sulfonyl chloride is shown as the following formula (I):
wherein X represents a perfluoro or semi-fluoroalkyl group of 1 to 5 carbon atoms.
As a preferred embodiment of the present invention, the alkyl sulfonyl fluoride includes, but is not limited to, trifluoromethane sulfonyl chloride and trifluoroethane sulfonyl chloride.
As a preferred embodiment of the present invention, the fluorinated aniline has a chemical structure represented by the following formula (II):
wherein R is1～R5Respectively represent fluorine atom or hydrogen atom, and can not be hydrogen atom at the same time.
In a preferred embodiment of the present invention, the organic solvent is at least one of dichloromethane, chloroform, carbon tetrachloride, acetone, diethyl carbonate, diethyl ether, ethylene glycol dimethyl ether, dimethyl carbonate, ethyl methyl carbonate, ethyl acetate, dioxolane, and acetonitrile.
In a preferred embodiment of the present invention, the acid-binding agent is at least one of formamide, triethylamine, pyridine, N-diisopropylethylamine, 4-dimethylaminopyridine, triethanolamine, and tetrabutylammonium bromide.
In a preferred embodiment of the present invention, the purification method includes solid-liquid separation, extraction, liquid separation, distillation, etc., the solid-liquid separation method is filtration or centrifugation, and the distillation method is distillation under reduced pressure.
In a preferred embodiment of the present invention, the molar mass ratio of the alkylsulfonyl fluoride to the fluoroaniline is 1 to 1.5:1, the amount of the solvent is 10 to 50 times the mass of the fluoroaniline, the mass ratio of the acid-binding agent to the organic solvent is 1:10 to 50, and the molar mass ratio of the salt ion of the salt-like substance to the fluoroaniline is 1 to 2: 1.
As a preferred embodiment of the invention, the reaction temperature is 0-80 ℃, the reaction time is 1-24 h, and the dropping speed is 1-5 ml/min.
The chemical structural formula of the synthesized alkylsulfonylfluoroaniline salt is shown as the following formula:
wherein X represents a perfluoro or semi-fluoroalkyl group of 1 to 5 carbon atoms, R1～R5Respectively represent fluorine atom or hydrogen atom, and not simultaneously hydrogen atom, M represents cation with valence of +1, and is selected from one of Li, Na and K.
The invention has the beneficial effects that:
1. the method has the advantages of mild reaction conditions, simple operation, and obviously simplified process, and is suitable for industrial production;
2. the yield is high, the product quality is good, the yield is more than 60%, and the product purity is more than 99%;
3. the method is green and environment-friendly, and the recycled solvent can be recycled, so that the generation of waste liquid is effectively reduced.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention. It is to be understood that the following description is only illustrative of the present invention and is not to be construed as limiting the present invention.
The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
The conjunction "consisting of …" excludes any unspecified elements, steps or components. If used in a claim, the phrase is intended to claim as closed, meaning that it does not contain materials other than those described, except for the conventional impurities associated therewith. When the phrase "consisting of …" appears in a clause of the subject matter of the claims rather than immediately after the subject matter, it defines only the elements described in the clause; other elements are not excluded from the claims as a whole.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range. In the present description and claims, range limitations may be combined and/or interchanged, including all sub-ranges contained therein if not otherwise stated.
The singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. "optional" or "any" means that the subsequently described event or events may or may not occur, and that the description includes instances where the event occurs and instances where it does not.
The indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the number clearly indicates the singular.
Further, the technical features of the embodiments of the present invention may be combined with each other as long as they do not conflict with each other.
The present invention will be further described with reference to specific examples, but the present invention should not be construed as being limited to these examples.
Example one
Pentafluoroaniline, trifluoromethanesulfonyl chloride and lithium hydroxide are used as raw materials to synthesize the alkylsulfonylfluoroaniline salt.
Weighing 9.15g of pentafluoroaniline, dissolving in 183.00g of dichloromethane, and adding 5.05g of triethylamine to prepare a mixed solution I; dissolving 9.27g of trifluoromethanesulfonyl chloride in 100.02g of dichloromethane to prepare a mixed solution II; and dropwise adding the mixed solution II into the mixed solution I under the protection of ice bath and nitrogen while stirring, wherein the dropwise adding time is 48min, and after the dropwise adding is finished, carrying out reflux reaction at 40 ℃ for 2 h. After the reaction is finished, filtering and separating the reactant, distilling the obtained organic filtrate at 40 ℃ under reduced pressure, and removing dichloromethane serving as a solvent and unreacted trifluoromethanesulfonyl chloride to obtain alkyl fluorophenol amine ester; dissolving alkyl fluoroaniline ester in 200.35g of dichloromethane to prepare a mixed solution III, mixing 1.32g of lithium hydroxide and 20.44g of dichloromethane to prepare a mixed solution IV, dropwise adding the mixed solution III into the mixed solution IV while stirring at normal temperature for 30min, and continuing to react for 3h at normal temperature after dropwise adding. After the reaction, filtration was carried out, solid-liquid separation was carried out, the filtrate was distilled under reduced pressure at 40 ℃ to obtain a solid, and the solid was dried at-0.09 MPa (relative to atmospheric pressure) at 60 ℃ for 24 hours to obtain 11.79g of a solid with a yield of 73.46% and a purity of 99.3% by ion chromatography.
Example two
The alkyl sulfonyl fluoride aniline salt is synthesized by using 2,3,4, 5-tetrafluoroaniline, trifluoroethane sulfonyl chloride and potassium hydroxide as raw materials.
Weighing 1.65g of 2,3,4, 5-tetrafluoroaniline, dissolving in 49.57g of dichloromethane, and adding 4.13g of formamide to prepare a mixed solution I; dissolving 2.72g of trifluoroethane sulfonyl chloride in 40.02g of dichloromethane to prepare a mixed solution II; and under the protection of ice bath and nitrogen, dropwise adding the mixed solution II into the mixed solution I while stirring, wherein the dropwise adding time is 30min, and after the dropwise adding is finished, carrying out reflux reaction at 30 ℃ for 8 h. After the reaction is finished, filtering and separating the reactant, distilling the obtained organic filtrate at 60 ℃ under reduced pressure, and removing dichloromethane serving as a solvent and trifluoroethane sulfonyl chloride which is not completely reacted to obtain alkyl fluorophenol amine ester; dissolving alkyl fluoroaniline ester in 80.89g of dichloromethane to prepare a mixed solution III, mixing 0.56g of potassium hydroxide and 12.64g of dichloromethane to prepare a mixed solution IV, dropwise adding the mixed solution III into the mixed solution IV while stirring at normal temperature for 10min, and continuing to react for 4h at normal temperature after dropwise adding. After the reaction, filtration was carried out, solid-liquid separation was carried out, the filtrate was distilled under reduced pressure at 40 ℃ to obtain a solid, and the solid was dried at 80 ℃ under-0.09 MPa (relative to atmospheric pressure) for 6 hours to obtain 2.39g of a solid with a yield of 68.75% and a purity of 99.5% by ion chromatography.
EXAMPLE III
The pentafluoroaniline, trifluoromethanesulfonyl chloride and sodium carbonate are used as raw materials to synthesize the alkylsulfonylfluoroaniline salt.
Weighing 9.15g of pentafluoroaniline, dissolving in 439.26g of dimethyl carbonate, and adding 10.03g of triethylamine to prepare a mixed solution I; dissolving 9.18g of trifluoromethanesulfonyl chloride in 103.70g of dimethyl carbonate to prepare a mixed solution II; and (3) dropwise adding the mixed solution II into the mixed solution I under the protection of ice bath and nitrogen while stirring, wherein the dropwise adding time is 50min, and after the dropwise adding is finished, carrying out reflux reaction at 25 ℃ for 18 h. After the reaction is finished, filtering and separating the reactant, distilling the obtained organic filtrate at 50 ℃ under reduced pressure, and removing a solvent dimethyl carbonate and unreacted trifluoromethanesulfonyl chloride to obtain alkyl fluorophenol amine ester; dissolving alkyl fluoroaniline ester in 198.58g of dichloromethane to prepare a mixed solution III, mixing 2.91g of anhydrous sodium carbonate and 20.44g of dimethyl carbonate to prepare a mixed solution IV, dropwise adding the mixed solution III into the mixed solution IV while stirring at normal temperature for 15min, and continuing to react for 6h at normal temperature after dropwise adding. After the reaction, the solution was filtered, solid-liquid separation was carried out, the filtrate was distilled under reduced pressure at 50 ℃ to obtain a solid, and the solid was dried at-0.09 MPa (relative to atmospheric pressure) at 40 ℃ for 24 hours to obtain 12.06g of a solid with a yield of 71.58% and a purity of 99.2% by ion chromatography.
Example four
3,4, 5-trifluoroaniline, perfluoroethylsulfonyl chloride and sodium hydroxide are used as raw materials to synthesize the alkylsulfonylfluoroaniline salt.
Weighing 3,4, 5-trifluoroaniline 6.46g, dissolving in carbon tetrachloride 77.85g, adding pyridine 3.89g, and preparing a mixed solution I; dissolving 11.75g of perfluoroethylsulfonyl chloride in 174.38g of carbon tetrachloride carbonate to prepare a mixed solution II; and (3) dropwise adding the mixed solution II into the mixed solution I under the protection of ice bath and nitrogen while stirring, wherein the dropwise adding time is 35min, and after the dropwise adding is finished, carrying out reflux reaction at 80 ℃ for 2 h. After the reaction is finished, filtering and separating the reactant, distilling the obtained organic filtrate at 35 ℃ under reduced pressure, and removing the solvent and unreacted perfluoroethylsulfonyl chloride to obtain the alkyl fluorophenol amine ester; dissolving alkyl fluoroanilide ester in 124.13g of carbon tetrachloride to prepare a mixed solution III, mixing 2.24g of sodium hydroxide and 34.32g of carbon tetrachloride to prepare a mixed solution IV, dropwise adding the mixed solution III into the mixed solution IV while stirring at normal temperature for 15min, and continuing to react for 12h at normal temperature after dropwise adding. After the reaction, filtration was carried out, solid-liquid separation was carried out, the filtrate was distilled under reduced pressure at 35 ℃ to obtain a solid, and the solid was dried at 50 ℃ under-0.09 MPa (relative to atmospheric pressure) for 18 hours to obtain 12.78g of a solid with a yield of 73.46% and a purity of 99.5% by ion chromatography.
EXAMPLE five
The alkyl sulfonyl fluoride aniline salt is synthesized by taking pentafluoroaniline, 3,3, 3-trifluoro propane sulfonyl chloride and lithium hydroxide as raw materials.
Weighing 7.32g of pentafluoroaniline, dissolving in 117.45g of diethyl ether, and adding 8.65g of triethanolamine to prepare a mixed solution I; 8.85g of 3,3, 3-trifluoropropanesulfonyl chloride is dissolved in 68.96g of diethyl ether to prepare a mixed solution II; and (3) dropwise adding the mixed solution II into the mixed solution I under the protection of ice bath and nitrogen while stirring, wherein the dropwise adding time is 30min, and after the dropwise adding is finished, carrying out reflux reaction at 40 ℃ for 3 h. After the reaction is finished, filtering and separating the reactant, distilling the obtained organic filtrate at 40 ℃ under reduced pressure, and removing the solvent and the unreacted trifluoromethanesulfonyl chloride to obtain the alkyl fluorophenol amine ester; dissolving alkyl fluoroaniline ester in 154.78g of diethyl ether to prepare a mixed solution III, mixing 1.08g of lithium hydroxide and 20.44g of diethyl ether to prepare a mixed solution IV, dropwise adding the mixed solution III into the mixed solution IV while stirring at normal temperature for 30min, and continuing to react for 4h at normal temperature after the dropwise addition. After the reaction, filtration was carried out, solid-liquid separation was carried out, the filtrate was distilled under reduced pressure at 40 ℃ to obtain a solid, and the solid was dried at 50 ℃ under-0.09 MPa (relative to atmospheric pressure) for 18 hours to obtain 9.31g of a solid with a yield of 65.98%, and the purity was 99.5% by ion chromatography.
EXAMPLE six
3, 4-difluoroaniline, trifluoromethanesulfonyl chloride and potassium hydroxide are used as raw materials to synthesize the alkylsulfonylfluoroanilide salt.
Weighing 3.87g of 3, 4-difluoroaniline, dissolving in 100.62g of acetone, and adding 7.65g of N, N-diisopropylethylamine to prepare a mixed solution I; dissolving 5.89g of trifluoromethanesulfonyl chloride in 56.34g of acetone to prepare a mixed solution II; and under the protection of ice bath and nitrogen, dropwise adding the mixed solution II into the mixed solution I while stirring, wherein the dropwise adding time is 30min, and after the dropwise adding is finished, carrying out reflux reaction at 30 ℃ for 4 h. After the reaction is finished, filtering and separating the reactant, distilling the obtained organic filtrate at 40 ℃ under reduced pressure, and removing the solvent and the unreacted trifluoromethanesulfonyl chloride to obtain the alkyl fluorophenol amine ester; dissolving alkyl fluoroaniline ester in 120.65g of acetone to prepare a mixed solution III, mixing 0.82g of lithium hydroxide and 19.87g of acetone to prepare a mixed solution IV, dropwise adding the mixed solution III into the mixed solution IV while stirring at normal temperature for 15min, and continuing to react for 2h at normal temperature after dropwise adding. After the reaction, filtration was carried out, solid-liquid separation was carried out, the filtrate was distilled under reduced pressure at 40 ℃ to obtain a solid, and the solid was dried at-0.09 MPa (relative to atmospheric pressure) at 40 ℃ for 8 hours to obtain 6.13g of a solid with a yield of 77.35% and a purity of 99.4% by ion chromatography.
EXAMPLE seven
3, 5-difluoroaniline, trifluoromethanesulfonyl chloride and potassium hydroxide are used as raw materials to synthesize the alkylsulfonylfluoroanilide salt.
Weighing 3.87g of 3, 5-difluoroaniline, dissolving in 100.62g of acetone, and adding 7.65g of N, N-diisopropylethylamine to prepare a mixed solution I; dissolving 5.89g of trifluoromethanesulfonyl chloride in 56.34g of acetone to prepare a mixed solution II; and under the protection of ice bath and nitrogen, dropwise adding the mixed solution II into the mixed solution I while stirring, wherein the dropwise adding time is 30min, and after the dropwise adding is finished, carrying out reflux reaction at 30 ℃ for 4 h. After the reaction is finished, filtering and separating the reactant, distilling the obtained organic filtrate at 40 ℃ under reduced pressure, and removing the solvent and the unreacted trifluoromethanesulfonyl chloride to obtain the alkyl fluorophenol amine ester; dissolving alkyl fluoroaniline ester in 120.65g of acetone to prepare a mixed solution III, mixing 0.82g of lithium hydroxide and 19.87g of acetone to prepare a mixed solution IV, dropwise adding the mixed solution III into the mixed solution IV while stirring at normal temperature for 15min, and continuing to react for 2h at normal temperature after dropwise adding. After the reaction, filtration was carried out, solid-liquid separation was carried out, the filtrate was distilled under reduced pressure at 40 ℃ to obtain a solid, and the solid was dried at-0.09 MPa (relative to atmospheric pressure) at 40 ℃ for 8 hours to obtain 5.96g of a solid with a yield of 75.25% and a purity of 99.5% by ion chromatography.
Example eight
3-fluoroaniline, trifluoromethanesulfonyl chloride and potassium carbonate are used as raw materials to synthesize the alkylsulfonylfluoroaniline salt.
Weighing 5.56g of 3-fluoroaniline, dissolving in 101.04g of acetonitrile, and adding 7.89g of tetrabutylammonium bromide to prepare a mixed solution I; dissolving 9.27g of trifluoromethanesulfonyl chloride in 98.56g of acetonitrile to prepare a mixed solution II; and (3) dropwise adding the mixed solution II into the mixed solution I under the protection of ice bath and nitrogen while stirring, wherein the dropwise adding time is 30min, and after the dropwise adding is finished, carrying out reflux reaction at 80 ℃ for 3 h. After the reaction is finished, filtering and separating the reactant, distilling the obtained organic filtrate at 60 ℃ under reduced pressure, and removing the solvent and unreacted trifluoromethanesulfonyl chloride to obtain the alkyl fluorophenol amine ester; dissolving alkyl fluoroaniline ester in 180.68g of acetonitrile to prepare a mixed solution III, mixing 3.80g of potassium carbonate and 31.35g of acetonitrile to prepare a mixed solution IV, dropwise adding the mixed solution III into the mixed solution IV while stirring at normal temperature for 20min, and continuing to react for 3h at 70 ℃ after the dropwise adding is finished. After the reaction, the mixture was filtered, subjected to solid-liquid separation, and the filtrate was subjected to reduced pressure distillation at 60 ℃ to obtain a solid, which was dried at-0.09 MPa (relative to atmospheric pressure) at 70 ℃ for 24 hours to obtain 9.55g of a solid with a yield of 66.95%, and a purity of 99.2% by ion chromatography.
Example nine
The alkyl sulfonyl fluoride aniline salt is synthesized by using 2, 6-difluoroaniline, trifluoroethane sulfonyl chloride and potassium hydroxide as raw materials.
Weighing 2, 6-difluoroaniline 6.46g, dissolving in dichloromethane 100.62g, adding triethylamine 7.65g, and preparing a mixed solution I; dissolving 10.04g of trifluoroethane sulfonyl chloride in 101.24g of dichloromethane to prepare a mixed solution II; and (3) dropwise adding the mixed solution II into the mixed solution I under the protection of ice bath and nitrogen while stirring, wherein the dropwise adding time is 30min, and after the dropwise adding is finished, carrying out reflux reaction at 40 ℃ for 6 h. After the reaction is finished, filtering and separating the reactant, distilling the obtained organic filtrate at 80 ℃ under reduced pressure, and removing the solvent and unreacted trifluoroethane sulfonyl chloride to obtain the alkyl fluorophenol amine ester; dissolving alkyl fluoroaniline ester in 132.79g dichloromethane to prepare a mixed solution III, mixing 3.09g potassium hydroxide and 54.68g dichloromethane to prepare a mixed solution IV, dropwise adding the mixed solution III into the mixed solution IV while stirring at normal temperature for 10min, and continuing to react for 4h at 40 ℃ after dropwise adding. After the reaction, filtration was carried out, solid-liquid separation was carried out, the filtrate was distilled under reduced pressure at 40 ℃ to obtain a solid, and the solid was dried at-0.09 MPa (relative to atmospheric pressure) at 40 ℃ for 8 hours to obtain 10.02g of a solid with a yield of 63.74% and a purity of 99.5% by ion chromatography.
Claims (9)
1. A preparation method of high-purity alkylsulfonylfluoroaniline salt is characterized by mixing fluoroaniline and an acid-binding agent in an organic solvent to prepare a mixed solution I, mixing alkylsulfonyl chloride and the organic solvent to prepare a mixed solution II, dropwise adding the mixed solution I into the mixed solution II under the condition of stirring, and after the reaction is finished, purifying to obtain alkylsulfonylfluoroaniline ester; dissolving the alkyl sulfonyl fluoroaniline ester in an organic solvent to form a mixed solution III, mixing inorganic or organic salt of a target salt to be prepared with the organic solvent to form a mixed solution IV, dropwise adding the mixed solution III into the mixed solution IV while stirring, reacting to obtain an alkyl sulfonyl fluoroaniline salt crude product, and removing impurities and purifying to obtain the high-purity alkyl sulfonyl fluoroaniline salt.
2. The method for preparing an alkylsulfonylfluoroanilide salt according to claim 1, wherein the alkylsulfonyl chloride has a chemical formula shown by the following formula (i):
wherein X represents a perfluoro or semi-fluoroalkyl group of 1 to 5 carbon atoms.
3. The method for preparing an alkylsulfonylfluoroaniline salt according to claim 1, wherein the fluoroaniline has a chemical formula represented by the following formula (II):
wherein R is1～R5Each represents a fluorine atomA proton or a hydrogen atom, and not both.
4. The method of claim 1, wherein the organic solvent is at least one of dichloromethane, chloroform, carbon tetrachloride, acetone, diethyl carbonate, diethyl ether, ethylene glycol dimethyl ether, dimethyl carbonate, methyl ethyl carbonate, ethyl acetate, dioxolane, and acetonitrile.
5. The method for preparing alkylsulfonylfluoroanilide salts according to claim 1, wherein said acid-binding agent is at least one of formamide, triethylamine, pyridine, N-diisopropylethylamine, 4-dimethylaminopyridine, triethanolamine, and tetrabutylammonium bromide.
6. The method for producing an alkylsulfonylfluoroanilide salt according to claim 1, wherein the purification method includes solid-liquid separation, extraction, liquid separation, distillation, or the like, the solid-liquid separation is filtration or centrifugation, and the distillation is distillation under reduced pressure.
7. The method for preparing an alkylsulfonylfluoroaniline salt according to claim 1, wherein the molar mass ratio of the alkylsulfonyl fluoride to the fluoroaniline is 1 to 1.5:1, the amount of the solvent is 10 to 50 times the mass of the fluoroaniline, the mass ratio of the acid-binding agent to the organic solvent is 1:10 to 50, and the molar mass ratio of the salt ions of the salt-like substance to the fluoroaniline is 1 to 2: 1.
8. The method for preparing the alkylsulfonylfluoroanilide salt according to claim 1, wherein the reaction temperature is 0 ℃ to 80 ℃, the reaction time is 1 to 24 hours, and the dropping rate is 1 to 5 ml/min.
9. The synthetic product of claims 1-8 having a formula as shown in formula iii:
wherein X represents a perfluoro or semi-fluoroalkyl group of 1 to 5 carbon atoms, R1～R5Respectively represent fluorine atom or hydrogen atom, and not simultaneously hydrogen atom, M represents cation with valence of +1, and is selected from one of Li, Na and K.
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| CN114573484A (en) * | 2022-03-04 | 2022-06-03 | 蜂巢能源科技股份有限公司 | Organic electrode material, intermediate thereof, positive plate and battery |
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