CN105967159A - Method for preparing lithium bis(fluorosulfonyl)imide from aromatic methyl amine - Google Patents

Method for preparing lithium bis(fluorosulfonyl)imide from aromatic methyl amine Download PDF

Info

Publication number
CN105967159A
CN105967159A CN201610281844.7A CN201610281844A CN105967159A CN 105967159 A CN105967159 A CN 105967159A CN 201610281844 A CN201610281844 A CN 201610281844A CN 105967159 A CN105967159 A CN 105967159A
Authority
CN
China
Prior art keywords
lithium
resin
reaction
amine
formula
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201610281844.7A
Other languages
Chinese (zh)
Other versions
CN105967159B (en
Inventor
金国范
金峰
王凯
张艳
张慧
李柳斌
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nanjing Yuanshu Medical Technology Co Ltd
Original Assignee
Nanjing Yuanshu Medical Technology Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nanjing Yuanshu Medical Technology Co Ltd filed Critical Nanjing Yuanshu Medical Technology Co Ltd
Priority to CN201610281844.7A priority Critical patent/CN105967159B/en
Publication of CN105967159A publication Critical patent/CN105967159A/en
Application granted granted Critical
Publication of CN105967159B publication Critical patent/CN105967159B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
    • C01B21/086—Compounds containing nitrogen and non-metals and optionally metals containing one or more sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/42—Introducing metal atoms or metal-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
    • C08G65/33303—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group
    • C08G65/33306—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group acyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/337—Polymers modified by chemical after-treatment with organic compounds containing other elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/28—Chemically modified polycondensates

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a method for preparing lithium bis(fluorosulfonyl)imide from aromatic methyl amine. The method comprises the following steps: dissolving aromatic methyl amine in an organic solvent, carrying out a sulfoamidation reaction on the obtained solution and to obtain bisfluorosulfonimide oxosulfuryl fluoride represented by formula ii, reducing bisfluorosulfonimide oxosulfuryl fluoride to obtain bis(fluorosulfonyl)imide represented by formula iii, and carrying out ion exchange on the bis(fluorosulfonyl)imide and resin lithium under an anhydrous solvent condition to obtain the final product lithium bis(fluorosulfonyl)imide. The method has the advantages of cheap and easily available raw materials, high yield, almost no pollution, no strict or dangerous reaction conditions, easy purification of the product, and suitableness for domestic mass production.

Description

A kind of method utilizing fragrance methyl ammonia to prepare imidodisulfuryl fluoride lithium salt
Technical field
The invention belongs to lithium ion battery electrolyte technical field, particularly relate to a kind of utilization fragrance double fluorine of methyl ammonia preparation The method of sulfimide lithium salts
Background technology
Double fluorine sulfimide lithium (LiN (SO2F)2, hereinafter referred to as LiFSI) and it is an electrolyte with wide application prospect Material, the conductivity of LiFSI is suitable, and heat stability, electrochemical stability are high；Occur side reaction probability little, HF will not be produced Deng corrosive gas, it it is indispensable new and high technology series products in current electrolyte of lithium-ion secondary battery.Along with lithium electricity row The development of industry, its market demand will be increasing, it is possible to grows into the star's product in auxiliary salt lithium salt compound.
The conventional synthetic method of double fluorine sulphonyl ammonia lithium salts mainly with ammonia, ammonium salt or ammonia as the source of ammonia, thereafter Add chlorosulfuric acid, or sulfuric chlorohydrin etc. synthesizes double chlorine sulphonyl ammonia lithium, then carry out fluorination and the double fluorine sulphonyl ammonia of lithiation gained Lithium salts, this type of method has some shortcoming following: 1) during industrial mass production, and the correct amount of ammonia is the mistake being difficult to sizing The most very few promote to generate unnecessary by-product, 2) a large amount of when using ammonia, it is easy to cause quick-fried at different temperatures and pressures Explode and make safety problem always for hidden danger.
Summary of the invention
The invention provides a kind of method utilizing fragrance methyl ammonia to prepare imidodisulfuryl fluoride lithium salt, the method raw material is honest and clean Valency is easy to get, and reactions steps is simple, and productivity is high, and almost without pollution, without unkind and dangerous reaction condition, product is easily purified, and is suitable for In domestic a large amount of productions.
In order to solve the problems referred to above, the technical solution adopted in the present invention is such, a kind of utilization fragrance methyl ammonia system The method of standby imidodisulfuryl fluoride lithium salt, comprises the following steps:
Fragrant methyl ammonia shown in formula is dissolved in organic solvent by A, and to carry out sulfonamide anti-with fluosulfonic acid or chlorine fluorine sulphonyl Should, obtain the double fluorine sulfonamide of the fragrant methyl shown in formula；
Step A is obtained the double fluorine sulfonamide of the fragrant methyl shown in formula and is dissolved in organic solvent, at catalyst action by B Under, obtain double fluorine sulphonyl ammonia through hydrogen reducing；
Double fluorine sulphonyl ammonia that step B is obtained by C and resin lithium are dissolved in organic solvent, carry out ion exchange and are finally produced Thing imidodisulfuryl fluoride lithium salt；
Wherein, R1=H, CH3, CH3CH2,R2=H, CH3, CH3CH2,
It is base catalyst that fragrant methyl ammonia shown in formula and chloro fluorine sulphonyl carry out the catalyst of sulfuryl amine reaction, institute The base catalyst stated is triethylamine, diisopropylethylamine, pyridine, sodium hydroxide, potassium hydroxide, sodium hydride, hydrofining, tertiary fourth Base sodium oxide or tert-butyl group potassium oxide, preferably triethylamine.
Fragrance methyl amine and chlorine fluorine sulphonyl shown in formula carry out sulfuryl amine reaction detailed process for will fragrance as shown Methyl amine and base catalyst are dissolved in organic solvent, after being cooled to 0～10 DEG C, are slowly added dropwise chlorine fluorine sulphonyl wherein, whole Keeping reaction temperature during dropping is 0～10 DEG C, is warming up to 20～35 DEG C after dropping, continues reaction 4～8h, reaction knot Shu Hou, reaction solution is through filtering, and filtrate, after decompression is distilled off solvent, adds ether sedimentation, again filters, the filtrate of collection After decompression is distilled off ether, through being recrystallized to give the double fluorine sulfonamide of the fragrant methyl shown in formula.
Fragrance methyl amine and fluosulfonic acid shown in formula carry out sulfuryl amine reaction detailed process will fragrance methyl as shown Amine is dissolved in organic solvent, is slowly added dropwise fluosulfonic acid wherein, and keeping reaction temperature during whole dropping is 20～40 DEG C, dropping After be warming up to 100～120 DEG C, continue reaction 8～24h, reaction terminate after, reaction solution through extraction, collect organic facies, will After the organic facies drying collected is distilled off solvent except water, decompression, it is recrystallized to give the double fluorine sulphur of the fragrant methyl shown in formula Amide.
The consumption of described chlorosulfonic acid or chlorine fluorine sulphonyl is 2.0～2.5:1 with the mol ratio of fragrance methyl amine shown in formula, It is preferably 2.2～2.5:1, more preferably 2.4～2.5:1.
As shown in fragrance methyl amine, preferably benzene methanamine, 4-methyl benzene methanamine, 3,5-dimethyl-benzyl amine.
In step B, being passed through hydrogen to pressure is 5～25psi, preferably 10～25psi, further preferred 20～25psi； The reduction reaction time is 4～12h, preferably 8～12h；It is preferably 10～25psi, more preferably 20～25psi；Reduction is anti- It is 4～12h between Ying Shi, preferably 8～12h；Reaction temperature is 25 DEG C～50 DEG C, preferably 25 DEG C～50 DEG C, and described catalyst is Metallic iron, metallic zinc, metallic copper, Metal Palladium, metal platinum, metallic nickel or palladium/carbon catalyst, the consumption of catalyst with as shown The mass ratio of fragrant methyl amine be 0.01～0.05:1, preferably 0.02～0.05:1, more preferably 0.03～0.05: 1。
The detailed process of step C, for double fluorine sulfonamide and resin lithium to be dissolved in respectively in organic solvent, forms double fluorine sulphonyl Amine aqueous solution and resin lithium solution, after resin lithium solution is cooled to-78～-50 DEG C, be slowly added dropwise double fluorine sulfonamide molten wherein Liquid, whole dropping process keeps reaction temperature to be-78～-50 DEG C, after dropping, in the situation that holding temperature is-78～-50 DEG C Under, continue reaction 2-4h, after having reacted, the reaction solution of gained after filtering, after decompression is distilled off solvent, heavily tie by filtrate Crystalline substance obtains double fluorine sulfonamide lithium salts.
Wherein, the consumption of described resin lithium is 1～5:1 with the mass ratio of double fluorine sulphonyl ammonia, preferably 3～5:1.
Wherein, the resin lithium described in step C is the resin lithium salts containing lithium ion with resin as Material synthesis, is existing Have, preferably the resin lithium as shown in formula (5), (6) (7) or (8),
Wherein, above-mentioned resin lithium uses following methods to be prepared from: containing N-methyl-iV-benzyl second in repetitive The resin of amide adds solvent organic amine and deacetylation reagent, under microwave irradiation, prepares resin amine；Then to institute The resin amine obtained adds organic solvent, reacts with the highly basic containing lithium and obtain resin lithium salts；Wherein, described deacetylation examination Agent is tetrabutyl ammonium fluoride, tetrabutylammonium chloride, tetrabutyl ammonium bromide, tetrabutylammonium iodide, ammonium iodide, ammonium fluoride, ammonium bromide Or ammonium chloride；
Described resin is one of following structure:
The reaction equation of the correspondingly resin lithium of the resins synthesis shown in formula (1) is as shown in formula I:
The reaction equation of the correspondingly resin lithium of the resins synthesis shown in formula (2) is as shown in formula II:
The reaction equation of the correspondingly resin lithium of the resins synthesis shown in formula (3) is as shown in formula III:
The reaction equation of the correspondingly resin lithium of the resins synthesis shown in formula (4) is as shown in formula IV:
The concrete preparation process of above-mentioned resin lithium is for join resin with solvent organic amine and deacetylation reagent Among sealed glass tube, under the microwave irradiation of 250-300W, it is warming up to 50-80 DEG C, reacts 5-60min, gained reaction solution After filtering, wash through acid solution, aqueous slkali and water successively, be dried to obtain resin amine；Add in the resin amine of gained Organic solvent, be cooled to-78～-50 DEG C after, be slowly added dropwise containing lithium highly basic wherein, rate of addition is 1～5mL/min, whole Maintain the temperature at-78～-50 DEG C during dropping, after dropping, keep temperature be-78～-50 DEG C under conditions of, continuation After reaction 2-4h, after having reacted, after filtering, filtrate is being distilled off molten-78～-50 DEG C through decompression the reaction solution of gained After agent, it is recrystallized to give double fluorine sulfonamide lithium salts.
Wherein, described is butyl lithium containing lithium highly basic, isobutyl group lithium, tert-butyl lithium, Lithamide., lithium hydride, diisopropyl Ammonia lithium or lithium metal.
The consumption of described deacetylation reagent and the mass ratio of resin are 0.8～1.5:1, preferably 0.8～ 1.3:1, more preferably 1～1.1:1；Described organic amine is selected from methyl amine, base amine, propyl group amine, methanediamine, base Diamidogen or propyl diamine, the consumption of organic amine and the mass ratio of resin are 4～6:1, preferably 5～5.5:1；
By resin-made for resin amine during, reaction temperature is preferably controlled to 70 DEG C～80 DEG C.
Prepared reaction temperature during resin lithium by resin amine and be preferably controlled to-78～-75 DEG C.
Described organic solvent is selected from dichloromethane, chloroform, oxolane, toluene, methanol, ethanol, the one in ether Or the mixture of two kinds of arbitrary proportions, the organic solvent described in above steps can be same, it is also possible to different, step In A, described organic solvent is preferably dichloromethane, chloroform, oxolane, a kind of or mixing of two kinds of arbitrary proportions in toluene Thing, more preferably chloromethanes, chloroform or toluene, the consumption of organic solvent is excellent with the mol ratio of fragrance methyl amine as shown Elect 5～15:1 as, more preferably 10～15:1；Organic solvent described in step B is preferably methanol, ethanol and tetrahydrochysene furan Mutter the middle a kind of or mixture of two kinds of arbitrary proportions；In step C, described organic solvent is preferably ether or oxolane；By During resin amine prepares resin lithium, described organic solvent is preferably ether or oxolane, its consumption and the quality of resin Ratio preferably 20～50:1, more preferably 40～50:1.
Beneficial effect: the method cheaper starting materials is easy to get, reactions steps is simple, and productivity is high, almost without pollution, without unkind danger Reaction condition, product is easily purified, and is suitable for domestic a large amount of production.
Detailed description of the invention
In order to deepen the understanding of the present invention, below in conjunction with embodiment, the invention will be further described, this embodiment It is only used for explaining the present invention, is not intended that limiting the scope of the present invention.
Embodiment 1
1) weighing 10g resin as shown in following formula (1), 10g ammonium bromide, 40g ethylenediamine joins among sealed glass tube, Under microwave irradiation, temperature rises to 80 DEG C of reaction 1h, and after completion of the reaction, temperature filters, with 400mL 1M HCL after being down to room temperature band Solution washs, and again again washs by 400mL 1M NaOH solution, finally washs with water 500mL, is dried and collects admittedly Body obtains 5.3g resin amine.
2) to step 1) the 5.3g resin amine of gained adds 250mL oxolane, it is then added in there-necked flask, temperature Being slowly added dropwise tert-butyl lithium 5.3mL after being down to-78 DEG C, rate of addition is 1.76mL/min, whole dropping process, keeps temperature For-78 DEG C～-75 DEG C, after dropping, in the case of keeping temperature to be-78 DEG C～-75 DEG C, continuing reaction 1h, question response is complete Bi Hou, fast direct takes over filter, after much filtrate being washed three times with 50mL oxolane (-78 DEG C～-75 DEG C), collects the filter obtained Going out thing, be resin lithium, altogether 4.2g, yield is disregarded.
Shown in the reaction equation following formula of the correspondingly resin lithium of the resins synthesis shown in formula (1):
Embodiment 2
1) weighing 10g resin as shown in following formula (2), 15g ammonium bromide, 50g ethylenediamine joins among sealed glass tube, Under microwave irradiation, temperature rises to 80 DEG C of reaction 1h, and after completion of the reaction, temperature filters, with 400mL 1M HCL after being down to room temperature band Solution washs, and again again washs by 400mL 1M NaOH solution, finally washs with water 400mL, is dried and collects admittedly Body obtains 5.1g resin amine.
2) adding 250mL oxolane in the 5.1g resin amine of gained, join in there-necked flask, temperature is down to-78 DEG C Being slowly added dropwise tert-butyl lithium 5.3mL afterwards, rate of addition is 1.76mL/min, whole dropping process, keeps temperature to be-78 DEG C ～-75 DEG C, after dropping, in the case of keeping temperature to be-78 DEG C～-75 DEG C, continue reaction 1h, after question response, soon Speed directly filters, and after much filtrate being washed three times with 50mL oxolane (-78 DEG C～-75 DEG C), collects the much filtrate obtained, i.e. For resin lithium salts, altogether 4.0g, yield is disregarded.
The reaction equation of the correspondingly resin lithium of the resins synthesis shown in formula (2) is shown below:
Embodiment 3
1) weighing 10g resin as shown in following formula (3), 9g ammonium bromide, 60g ethylenediamine joins among sealed glass tube, Under microwave irradiation, temperature rises to 80 DEG C of reaction 1h, and after completion of the reaction, temperature filters, with 400mL 1M HCL after being down to room temperature band Solution washs, and again again washs by 450mL 1M NaOH solution, finally washs with water 500mL, is dried and collects admittedly Body obtains 5.5g resin amine.
2) to step 1) the 5.1g resin amine of gained adds 250mL oxolane, join in there-necked flask, temperature drops Being slowly added dropwise tert-butyl lithium 5.8mL after-78 DEG C, rate of addition is 1.76mL/min, whole dropping process, keeps temperature For-78 DEG C～-75 DEG C, after dropping, in the case of keeping temperature to be-78 DEG C～-75 DEG C, continuing reaction 1h, question response is complete Bi Hou, fast direct takes over filter, after much filtrate being washed three times with 50mL oxolane (-78 DEG C～-75 DEG C), collects the filter obtained Going out thing, be resin amine, altogether 4.1g, yield is disregarded.
The reaction equation of the correspondingly resin lithium of the resins synthesis shown in formula (3) is shown below:
Embodiment 4
1) weighing 10g resin as shown in following formula (4), 12g ammonium bromide, 40g ethylenediamine joins among sealed glass tube, Under microwave irradiation, temperature rises to 80 DEG C of reaction 1h, and after completion of the reaction, temperature filters, with 400mL 1M HCL after being down to room temperature band Solution washs, and again again washs by 400mL 1M NaOH solution, finally washs with water 400mL, is dried and collects admittedly Body obtains 5.0g resin amine.
2) to step 1) the 5.0g resin amine of gained adds 250mL oxolane, join in there-necked flask, temperature drops Being slowly added dropwise tert-butyl lithium 5.3mL after-78 DEG C, rate of addition is 1.76mL/min, whole dropping process, keeps temperature For-78 DEG C～-75 DEG C, after dropping, in the case of keeping temperature to be-78 DEG C～-75 DEG C, continuing reaction 1h, question response is complete Bi Hou, fast direct takes over filter, after much filtrate being washed three times with 50mL oxolane (-78 DEG C～-75 DEG C), collects the filter obtained Going out thing, be resin lithium, altogether 4.4g, yield is disregarded.
The reaction equation of the correspondingly resin lithium of the resins synthesis shown in formula (4) is shown below:
In embodiment 1-4, the resin such as formula (1) (2) (3) and (4) is existing, and it is bought in Korea S KUKDO ChemicaL or Korea S KANGNAM Chem.
Embodiment 5
1) weigh 10.7g benzene methanamine, after 8.13mL triethylamine is dissolved in chloroform 800mL, join with constant pressure funnel With in the there-necked flask of thermometer, temperature is slowly added dropwise chlorine fluorine sulphonyl 18.22mL after being down to 0 DEG C, and time for adding is 1h, whole Add reaction temperature and be maintained at 0 DEG C～5 DEG C, after dropping, be warming up to 35 DEG C, continue reaction 4h, band after completion of the reaction, by gained Reactant liquor filter, collect filtrate after decompression is distilled off chloroform, add after ether 500mL is stirred at room temperature 1h, Again filter, collect filtrate through decompression ether is distilled off after, add n-hexane 50mL be recrystallized to give 26.54g benzyl Double fluorine sulfonamide, yield 98%, in terms of benzene methanamine.
2) weigh after the double fluorine sulfonamide of 26.54g benzyl is dissolved in 800mL oxolane/ethanol (volume ratio is 1:1), Join among hydrogen reactor, add 0.94g palladium/carbon (mass fraction of palladium is 10%) catalyst, carry and ready slowly lead Entering hydrogen, pressure controls at 20psi, and temperature slowly regulates to 40 DEG C every 1h from 25 DEG C, and the response time is 10h, and band has reacted After Bi Wendu is down to room temperature, directly filtering, much filtrate 50mL oxolane washs three times, reclaims metallic catalyst, Collection obtains filtrate after decompression distillation, adds n-hexane 50mL and is recrystallized to give the double fluorine sulfonamide of 15.77g, and yield is 89%, In terms of the double fluorine sulfonamide of benzyl.
3) weigh the double fluorine sulfonamide of 15.77g to be dissolved in oxolane 500mL and form double fluorine sulfonamide solution, weigh 22g and implement Resin lithium prepared by 1 is dissolved in oxolane 20mL formation resin lithium solution and joins in there-necked flask, and its temperature is down to-78 DEG C Afterwards, being slowly added dropwise double fluorine sulfonamide solution wherein, time for adding is 1h, whole drip reacting temperature be maintained at-78 DEG C～- 75 DEG C, after dropping ,-78 DEG C～-75 DEG C are continued reaction 2h, after question response, after question response, whole post processing Journey is carried out in the case of-78 DEG C～-75 DEG C and solvent for use uses after being cooled to-78 DEG C～-75 DEG C, and concrete process is: Fast direct connects filtering reacting liquid, and much filtrate 50mL oxolane washs three times, in order to reclaim the resin lithium of excess；Collect filter Liquid is after decompression is distilled off solvent, and after addition ether 200mL is stirred at room temperature 1h, the solid being filtrated to get is washed through 50mL ether After washing three times, obtaining double fluorine sulfonamide lithium salts 12.8g, yield is disregarded.
Concrete reaction equation is shown below:
Embodiment 6
1) weigh 10.7g benzene methanamine and be dissolved among 800mL toluene, add with constant pressure funnel and three mouthfuls of thermometer In Ping, being slowly added dropwise 5.3mL fluosulfonic acid at 25 DEG C, time for adding is 30 minutes, is warming up to 110 DEG C after dropping, continues Reaction 8h, band reacts complete temperature and is down to room temperature, add 100mL saturated solution of sodium carbonate and 500mL distilled water extracts, collects Organic facies, adds magnesium sulfate in the organic facies collected and is dried it, filter, and the filtrate of collection is distilled off molten through decompression After agent, adding n-hexane 50mL and be recrystallized to give the double fluorine sulfonamide of 24.57g benzyl, yield (in terms of benzene methanamine) is 91%.
2) weigh the double fluorine sulfonamide of 24.57g benzyl and be dissolved in mixture (both volumes of 8000mL oxolane and ethanol Than 1:1) in, joining among hydrogen reactor, add 0.87g palladium/carbon (mass fraction of palladium is 10%) catalyst, band has prepared Finishing and slowly import hydrogen, general pressure controls at 20psi, and temperature is adjusted up 3 DEG C to 40 DEG C from 25 DEG C every 1h, the response time For 10h, after the complete temperature of band reaction is down to room temperature, filtering, much filtrate 50mL oxolane washs it three times, reclaims metal and urges Agent, filtrate, after decompression distillation, adds n-hexane 50mL and is recrystallized to give the double fluorine sulfonamide of 13.7g, and yield is (double with benzyl Fluorine sulfonamide meter) it is 84%.
3) weigh the double fluorine sulfonamide of 13.7g to be dissolved in oxolane 500mL and form double fluorine sulfonamide solution, weigh 20g and implement Resin lithium prepared by example 2 is dissolved in oxolane 20mL formation resin lithium solution and adds to there-necked flask, is slowly added dropwise wherein Double fluorine sulfonamide solution, time for adding is 1h, and whole drip reacting temperature is maintained at-78～-75 DEG C, after dropping ,-78 ～at-75 DEG C, continuing reaction 2h, after question response, after question response, whole last handling process is-78 DEG C～-75 DEG C of feelings Carry out under condition and solvent for use be cooled to-78 DEG C～-75 DEG C after use, concrete process is: fast direct connects filtering reacting liquid, Much filtrate 50mL oxolane washs three times, in order to reclaim the resin lithium of excess；Collect filtrate and be distilled off molten through decompression After agent, after addition 200mL ether is stirred at room temperature 1h, the solid being filtrated to get, after 50mL ether washs three times, obtains double fluorine sulphur Amide lithium salts 11.3g, yield is disregarded.
Concrete reaction equation is shown below:
Embodiment 7
1) weigh 13.5g 3,5-dimethyl-benzyl amine, after 41.7mL triethylamine is dissolved in chloroform 800mL, join band persevering In the there-necked flask of pressure Dropping funnel and thermometer, temperature is slowly added dropwise chlorine fluorine sulphonyl 18.27mL, time for adding after being down to 0 DEG C For 1h, whole drip reacting temperature is maintained at 0 DEG C-5 DEG C, is warming up to 35 DEG C after dropping, continues reaction 4h, and band reaction is complete After, directly filter, collect filtrate after decompression is distilled off chloroform, add after ether 500mL is stirred at room temperature 1h, mistake Filter, collect obtain filtrate through decompression ether is distilled off after, add n-hexane 50mL be recrystallized to give 27.8g 3,5-dimethyl The double fluorine sulfonamide of benzyl, yield (in terms of benzene methanamine) is 93%.
2) weighing 27.8g 3, the double fluorine sulfonamide of 5-dimethyl benzyl is dissolved in the mixing of 8000mL oxolane and ethanol After in thing (both volume ratios 1:1), join among hydrogen reactor, add 0.92g palladium/carbon (mass fraction of palladium is 10%), Carrying ready slow importing hydrogen, pressure controls at 20psi, and temperature slowly regulates to 40 DEG C every 1h from 25 DEG C, during reaction Between be 10h, band reacts after complete temperature is down to room temperature, filters, and much filtrate 50mL oxolane washs three times, reclaims metal and urges Agent, filtrate, after decompression is distilled off solvent, adds n-hexane 50mL and is recrystallized to give the double fluorine sulfonamide of 12.45g, yield (with 3, the double fluorine sulfonamide meter of 5-dimethyl benzyl) are 72%.
3) weigh the double fluorine sulfonamide of 12.45g to be dissolved in oxolane 500mL and form double fluorine sulfonamide solution, weigh 13.6g real Execute the resin lithium prepared by 3 be dissolved in oxolane 20mL formed resin lithium solution join in there-necked flask, its temperature is down to-78 After DEG C, being slowly added dropwise double fluorine sulfonamide solution wherein, time for adding is 1h, whole drip reacting temperature be maintained at-78～- 75 DEG C, after dropping-78～-75 DEG C continue reaction 2h, band after completion of the reaction, after question response, whole last handling process Carrying out in the case of-78 DEG C～-75 DEG C and solvent for use uses after being cooled to-78 DEG C～-75 DEG C, concrete process is: fast Speed directly filtering reacting liquid, much filtrate 50mL oxolane washs three times, in order to reclaim the resin lithium of excess；Collect filtrate After decompression is distilled off solvent, after addition 200mL ether is stirred at room temperature 1h, the solid being filtrated to get washs three through 50mL ether After secondary, collect mother solution and obtain the double fluorine sulfonamide lithium salts of 10.5g, yield (in terms of double fluorine sulfonamide) 82% through decompression distillation.
Concrete reaction equation is shown below:
Embodiment 8
Same as in Example 5, except for the difference that step 5) in, the resin lithium used is the resin lithium described in embodiment 4, warp After collection, obtaining the double fluorine sulfonamide lithium salts of 10.6g benzyl, yield is disregarded.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all essences in the present invention Within god and principle, any modification, equivalent substitution and improvement etc. made, should be included within the scope of the present invention.

Claims (10)

1. one kind utilizes the method that fragrance methyl ammonia prepares imidodisulfuryl fluoride lithium salt, it is characterised in that comprise the following steps:
Fragrant methyl ammonia shown in formula is dissolved in organic solvent by A, carries out sulfuryl amine reaction with fluosulfonic acid or chlorine fluorine sulphonyl, To the double fluorine sulfonamide of the fragrant methyl shown in formula；
Step A is obtained the double fluorine sulfonamide of the fragrant methyl shown in formula and is dissolved in organic solvent by B, under catalyst action, and warp Hydrogen reducing obtains double fluorine sulphonyl ammonia；
Double fluorine sulphonyl ammonia and resin lithium that step B is obtained by C are dissolved in organic solvent respectively, carry out ion exchange and are finally produced Thing imidodisulfuryl fluoride lithium salt；
Wherein, R1=H, CH3,CH3CH2,R2=H, CH3,CH3CH2,
2. require a kind of described method utilizing fragrance methyl ammonia to prepare imidodisulfuryl fluoride lithium salt according to claim 1, its Being characterised by, it is base catalyst that the fragrant methyl ammonia shown in formula and chlorine fluorine sulphonyl carry out the catalyst of sulfuryl amine reaction, described Base catalyst be triethylamine, diisopropylethylamine, pyridine, sodium hydroxide, potassium hydroxide, sodium hydride, hydrofining, the tert-butyl group Sodium oxide or tert-butyl group potassium oxide.
A kind of method utilizing fragrance methyl ammonia to prepare imidodisulfuryl fluoride lithium salt the most according to claim 2, its feature Being, fragrance methyl amine shown in formula and chlorine fluorine sulphonyl carry out the detailed process of sulfuryl amine reaction for by fragrance methyl amine shown in formula Being dissolved in organic solvent with base catalyst, after being cooled to 0～10 DEG C, dropping chlorine fluorine sulphonyl wherein, during whole dropping Keeping reaction temperature is 0～10 DEG C, is warming up to 20～35 DEG C after dropping, continues reaction 4～8h, after reaction terminates, and reaction Solution is through filtering, and filtrate, after decompression is distilled off organic solvent, adds ether sedimentation, again filters, and the filtrate of collection is through subtracting After pressure is distilled off ether, through being recrystallized to give the double fluorine sulfonamide of the fragrant methyl shown in formula.
A kind of method utilizing fragrance methyl ammonia to prepare imidodisulfuryl fluoride lithium salt the most according to claim 1, its feature Be, fragrance methyl amine and fluosulfonic acid shown in formula carry out sulfuryl amine reaction detailed process by molten for methyl amine fragrant shown in formula In organic solvent, being slowly added dropwise fluosulfonic acid wherein, keeping reaction temperature during whole dropping is 20～40 DEG C, drips complete After be warming up to 100～120 DEG C, continue reaction 8～24h, reaction terminate after, reaction solution through extraction, collect organic facies, collection After organic facies drying is distilled off organic solvent except water, decompression, it is recrystallized to give the double fluorine sulphonyl of the fragrant methyl shown in formula Amine.
A kind of method utilizing fragrance methyl ammonia to prepare imidodisulfuryl fluoride lithium salt the most according to claim 1, its feature Being, the consumption of described fluosulfonic acid or chlorine fluorine sulphonyl is 2.0～2.5:1 with the mol ratio of fragrance methyl amine as shown.
A kind of method utilizing fragrance methyl ammonia to prepare imidodisulfuryl fluoride lithium salt the most according to claim 1, its feature Being, in step B, being passed through hydrogen to pressure is 5～25psi.
A kind of method utilizing fragrance methyl ammonia to prepare imidodisulfuryl fluoride lithium salt the most according to claim 1, its feature Being, the detailed process of step C, for double fluorine sulfonamide and resin lithium to be dissolved in respectively in anhydrous solvent, forms double fluorine sulfonamide Solution and resin lithium solution, after resin lithium solution is cooled to-78～-50 DEG C, be slowly added dropwise double fluorine sulfonamide solution wherein, Whole dropping process keeps reaction temperature to be-78～-50 DEG C, after dropping, holding temperature be-78～-50 DEG C in the case of, Continuing reaction 2～4h, after having reacted, the reaction solution of gained after filtering, remove through decompression distillation at-78～-50 DEG C by filtrate After removing solvent, it is recrystallized to give double fluorine sulfonamide lithium salts.
A kind of method utilizing fragrance methyl ammonia to prepare imidodisulfuryl fluoride lithium salt the most according to claim 1, its feature Being, wherein, the resin lithium described in step C uses following methods to be prepared from: containing N-methyl-N-benzene in repetitive The resin of methylacetamide adds solvent organic amine and deacetylation reagent, under microwave irradiation, prepares resin amine；So The resin amine of backward gained adds organic solvent, reacts with the highly basic containing lithium and obtain resin lithium salts；Wherein, described deacetylated Reaction reagent is tetrabutyl ammonium fluoride, tetrabutylammonium chloride, tetrabutyl ammonium bromide, tetrabutylammonium iodide, ammonium iodide, ammonium fluoride, Ammonium bromide or ammonium chloride；
Described resin is one of following structure:
The preparation method of imidodisulfuryl fluoride lithium salt the most according to claim 8, it is characterised in that the concrete system of resin lithium Standby process is for joining among sealed glass tube, 250-300W's by resin with solvent organic amine and deacetylation reagent Under microwave irradiation, be warming up to 50-80 DEG C, react 5-60min, gained reaction solution after filtering, successively through acid solution, aqueous slkali Wash with water, be dried to obtain resin amine；In the resin amine of gained add organic solvent, be cooled to-78～-50 DEG C after, Being slowly added dropwise containing lithium highly basic wherein, rate of addition is 4～5mL/min, maintains the temperature at-78～-50 during whole dropping DEG C, after dropping, keep temperature be-78～-50 DEG C under conditions of, continue to react after 2-4h, after the reaction solution of gained Through filtering, after washing, obtain resin amine lithium.
The preparation method of a kind of resin lithium the most according to claim 8, it is characterised in that described is fourth containing lithium highly basic Base lithium, isobutyl group lithium, tert-butyl lithium, Lithamide., lithium hydride, diisopropyl ammonia lithium or lithium metal.
CN201610281844.7A 2016-04-29 2016-04-29 A kind of method for preparing imidodisulfuryl fluoride lithium salt using fragrant methyl amine Active CN105967159B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610281844.7A CN105967159B (en) 2016-04-29 2016-04-29 A kind of method for preparing imidodisulfuryl fluoride lithium salt using fragrant methyl amine

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610281844.7A CN105967159B (en) 2016-04-29 2016-04-29 A kind of method for preparing imidodisulfuryl fluoride lithium salt using fragrant methyl amine

Publications (2)

Publication Number Publication Date
CN105967159A true CN105967159A (en) 2016-09-28
CN105967159B CN105967159B (en) 2018-06-01

Family

ID=56993604

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610281844.7A Active CN105967159B (en) 2016-04-29 2016-04-29 A kind of method for preparing imidodisulfuryl fluoride lithium salt using fragrant methyl amine

Country Status (1)

Country Link
CN (1) CN105967159B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116120187A (en) * 2023-04-17 2023-05-16 研峰科技(北京)有限公司 Method for synthesizing lithium diisopropylamide serving as large-steric-hindrance organic base
CN116462165A (en) * 2023-04-28 2023-07-21 湖北兴发化工集团股份有限公司 Preparation method of lithium bis (fluorosulfonyl) imide

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011065502A1 (en) * 2009-11-27 2011-06-03 株式会社日本触媒 Fluorosulfonyl imide salt and method for producing fluorosulfonyl imide salt
CN103524387A (en) * 2013-10-25 2014-01-22 中国海洋石油总公司 Preparation method of imidodisulfuryl fluoride lithium salt
CN104495767A (en) * 2014-11-21 2015-04-08 湖南有色郴州氟化学有限公司 Preparation method of lithium bis(fluorosulfonyl)amide
WO2015082519A1 (en) * 2013-12-05 2015-06-11 Rhodia Operations Method for producing a fluorine- and sulphur-bearing compound and salts thereof in an aqueous medium
CN104925765A (en) * 2015-05-21 2015-09-23 上海康鹏化学有限公司 Preparation method for difluorosulfimide lithium salt

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011065502A1 (en) * 2009-11-27 2011-06-03 株式会社日本触媒 Fluorosulfonyl imide salt and method for producing fluorosulfonyl imide salt
CN103524387A (en) * 2013-10-25 2014-01-22 中国海洋石油总公司 Preparation method of imidodisulfuryl fluoride lithium salt
WO2015082519A1 (en) * 2013-12-05 2015-06-11 Rhodia Operations Method for producing a fluorine- and sulphur-bearing compound and salts thereof in an aqueous medium
CN104495767A (en) * 2014-11-21 2015-04-08 湖南有色郴州氟化学有限公司 Preparation method of lithium bis(fluorosulfonyl)amide
CN104925765A (en) * 2015-05-21 2015-09-23 上海康鹏化学有限公司 Preparation method for difluorosulfimide lithium salt

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116120187A (en) * 2023-04-17 2023-05-16 研峰科技(北京)有限公司 Method for synthesizing lithium diisopropylamide serving as large-steric-hindrance organic base
CN116462165A (en) * 2023-04-28 2023-07-21 湖北兴发化工集团股份有限公司 Preparation method of lithium bis (fluorosulfonyl) imide

Also Published As

Publication number Publication date
CN105967159B (en) 2018-06-01

Similar Documents

Publication Publication Date Title
CN106365132A (en) Preparation method of difluoro-sulfimide and lithium difluoro-sulfimide
CN104495767A (en) Preparation method of lithium bis(fluorosulfonyl)amide
CN105731398B (en) Preparation method of alkali metal salt of bis (fluorosulfonyl) imide
CN106276829B (en) A kind of synthetic method of double fluorine sulfimide lithiums
CN105949093B (en) A kind of preparation method of double trifluoromethanesulfonimide lithium salts
CN111483986A (en) Preparation method of lithium bis (fluorosulfonyl) imide and lithium bis (fluorosulfonyl) imide
WO2022262175A1 (en) Lithium bis(fluorosulfonyl)imide, preparation method therefor and application thereof
CN105858626B (en) A preparing method of lithium bis(fluorosulfonyl)imide
JP5402634B2 (en) Process for producing purified ammonium salt of fluorine-containing bissulfonylimide
CN105967159A (en) Method for preparing lithium bis(fluorosulfonyl)imide from aromatic methyl amine
CN105923614B (en) A kind of method that imidodisulfuryl fluoride lithium salt is prepared using phthalimide
CN105836719B (en) A kind of method for synthesizing imidodisulfuryl fluoride lithium salt using fragrant methyl amine
JP2020147558A (en) Preparation method of high-purity lithium salt by mixture in predetermined ratio and applications of the lithium salt
CN105948000B (en) A kind of method that imidodisulfuryl fluoride lithium salt is prepared using fragrant methyl azide
CN110759884B (en) Method for co-producing fluoroethylene carbonate and vinylene carbonate
CN105905875B (en) A kind of method that imidodisulfuryl fluoride lithium salt is prepared using hydrazine
CN105948001B (en) A kind of method that imidodisulfuryl fluoride lithium salt is prepared using hydroxyl ammonia
CN116283601A (en) Preparation method of difluoro sulfonimide organic ammonium salt
CN116621150A (en) Preparation method of sodium difluorophosphate
KR101687374B1 (en) Method for producing difluorosulfonyl imide or its salt
CN107244662B (en) A kind of preparation method of bis- (fluorosulfonyl) imides
CN109369474B (en) Preparation method of lithium bis (trifluoromethylsulfonyl) imide
CN103253688B (en) Method for preparing high-purity lithium fluoride and lithium hexafluorophosphate by utilization of organo tin fluoride
CN103732587A (en) Double-center bipyridyl cationic ion liquid, preparation method therefor and use thereof
CN102180816A (en) Preparation method of asymmetric type bi-fluoro sulfimide potassium

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant