CN105967159B - A kind of method for preparing imidodisulfuryl fluoride lithium salt using fragrant methyl amine - Google Patents

A kind of method for preparing imidodisulfuryl fluoride lithium salt using fragrant methyl amine Download PDF

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CN105967159B
CN105967159B CN201610281844.7A CN201610281844A CN105967159B CN 105967159 B CN105967159 B CN 105967159B CN 201610281844 A CN201610281844 A CN 201610281844A CN 105967159 B CN105967159 B CN 105967159B
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resin
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CN105967159A (en
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金国范
金峰
王凯
张艳
张慧
李柳斌
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Nanjing Yuanshu Medical Technology Co Ltd
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
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    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
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    • 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
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/28—Chemically modified polycondensates

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Abstract

The invention discloses a kind of methods for preparing imidodisulfuryl fluoride lithium salt using fragrant methyl ammonia, comprise the following steps, fragrant methyl ammonia is dissolved in organic solvent, sulfuryl amine reaction is carried out with fluosulfonic acid or chloro fluorine sulphonyl, obtain the double fluorine sulfonamide of fragrant methyl, it obtains double fluorine sulphonyl ammonia under catalyst action, through hydrogen reducing；By double fluorine sulphonyl ammonia of gained, under the conditions of anhydrous solvent, carry out ion exchange with resin lithium and obtain final product imidodisulfuryl fluoride lithium salt；This method raw material is cheap and easy to get, and reaction step is simple, and yield is high, and almost pollution-free, without unkind and dangerous reaction condition, product is easily purified, and is suitable for domestic mass production.

Description

A kind of method for preparing imidodisulfuryl fluoride lithium salt using fragrant methyl amine
Technical field
The invention belongs to lithium ion battery electrolyte technical fields more particularly to a kind of fragrant methyl amine of utilization to prepare double fluorine 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 Substance, the conductivity of LiFSI is suitable, and thermal stability, electrochemical stability are high；Generation side reaction probability is small, will not generate HF Corrosive gas are waited, are indispensable new and high technology class products in current electrolyte of lithium-ion secondary battery.With lithium electricity row The continuous development of industry, the market demand will be increasing, it is possible to star's product supplemented by growth in salt lithium salt compound.
The previous synthetic method of double fluorine sulphonyl ammonia lithium salts is mainly with the source of ammonium hydroxide, ammonium salt or ammonia as ammonia, thereafter It adds in chlorosulfuric acid or sulfuric chlorohydrin etc. and synthesizes double chlorine sulphonyl ammonia lithiums, then carry out double fluorine sulphonyl ammonia obtained by fluorination and lithiation Lithium salts, such method have following shortcoming：1) during industrial mass production, it is difficult the mistake shaped that the correct amount of ammonia, which is, Mostly very few to promote to generate unnecessary by-product, 2) when largely using ammonia, it is easy to cause at different temperatures and pressures quick-fried It is fried so that safety problem is hidden danger always.
The content of the invention
The present invention provides a kind of method for preparing imidodisulfuryl fluoride lithium salt using fragrant methyl amine, this method raw material is honest and clean Valency is easy to get, and reaction step is simple, and yield is high, and almost pollution-free, without unkind and dangerous reaction condition, product is easily purified, and is suitble to In domestic mass production.
To solve the above-mentioned problems, the technical solution adopted in the present invention is such a kind of fragrant methyl amine system of utilization The method of standby imidodisulfuryl fluoride lithium salt, comprises the following steps：
Fragrant methyl amines of the A shown in by formula I is dissolved in organic solvent, and it is anti-to carry out sulfonamide with fluosulfonic acid or chlorine fluorine sulphonyl Should, obtain the double fluorine sulfonamide of fragrant methyl shown in formula II；
The double fluorine sulfonamide of fragrant methyl that step A is obtained shown in formula II by B are dissolved in organic solvent, in catalyst action Under, obtain double fluorine sulphonyl ammonia through hydrogen reducing；
Double fluorine sulphonyl ammonia that C obtains step B are dissolved in resin lithium in organic solvent, are carried out ion exchange and are finally produced Object imidodisulfuryl fluoride lithium salt；
Wherein, R1=H, CH3, CH3CH2,R2=H, CH3, CH3CH2,
Fragrant methyl amine shown in formula I carries out the catalyst of sulfuryl amine reaction as basic catalyst with chloro fluorine sulphonyl, institute The basic catalyst stated be triethylamine, diisopropylethylamine, pyridine, sodium hydroxide, potassium hydroxide, sodium hydride, hydrofining, tertiary fourth Base sodium oxide molybdena or tertiary butyl potassium oxide are preferably triethylamine.
Fragrant methyl amine shown in formula I and the detailed process of chlorine fluorine sulphonyl progress sulfuryl amine reaction are will be fragrant as shown in I Methyl amine and basic catalyst are dissolved in organic solvent, after being cooled to 0~10 DEG C, chlorine fluorine sulphonyl are slowly added dropwise thereto, entirely It is 0~10 DEG C that reaction temperature is kept during being added dropwise, and 20~35 DEG C are warming up to after being added dropwise, the reaction was continued 4~8h, reaction knot Shu Hou, reaction solution is filtered, and filtrate adds in ether precipitation, filter again, the filtrate of collection after vacuum distillation removes solvent After vacuum distillation removes ether, the double fluorine sulfonamide of fragrant methyl through being recrystallized to give shown in formula II.
Fragrant methyl amine shown in formula I and fluosulfonic acid carry out the detailed process of sulfuryl amine reaction for will as shown in I fragrant methyl Amine is dissolved in organic solvent, and fluosulfonic acid is slowly added dropwise thereto, and entire be added dropwise keeps reaction temperature to be added dropwise for 20~40 DEG C in the process After be warming up to 100~120 DEG C, the reaction was continued 8~for 24 hours, and after reaction, reaction solution collects organic phase through extraction, will The organic phase of collection is recrystallized to give the double fluorine sulphurs of fragrant methyl shown in formula II after dry water removal, vacuum distillation remove solvent Amide.
The molar ratio of the chlorosulfonic acid or the dosage of chlorine fluorine sulphonyl and fragrant methyl amine shown in formula I is 2.0~2.5：1, Preferably 2.2~2.5：1, more preferably 2.4~2.5：1.
It is preferably benzene methanamine in the fragrant methyl amine as shown in I, 4- methyl benzene methanamines, 3,5- dimethyl-benzyl amines.
In step B, it is 5~25psi to be passed through hydrogen to pressure, is preferably 10~25psi, further preferred 20~25psi； The reduction reaction time is 4~12h, preferably 8~12h；Preferably 10~25psi, further preferably 20~25psi；Reduction is anti- It is 4~12h, preferably 8~12h between seasonable；Reaction temperature is 25 DEG C~50 DEG C, and preferably 25 DEG C~50 DEG C, the catalyst is Metallic iron, metallic zinc, metallic copper, Metal Palladium, metal platinum, metallic nickel or palladium/carbon catalyst, the dosage of catalyst with as shown in I Fragrant methyl amine mass ratio be 0.01~0.05：1, it is preferably 0.02~0.05：1, further preferably 0.03~0.05： 1。
The detailed process of step C forms double fluorine sulphonyl for double fluorine sulfonamide and resin lithium are dissolved in organic solvent respectively After resin lithium solution is cooled to -78~-50 DEG C, it is molten that double fluorine sulfonamide are slowly added dropwise in amine aqueous solution and resin lithium solution thereto Liquid, the entire process that is added dropwise keeps reaction warm for -78~-50 DEG C, after being added dropwise, is keeping the situation that temperature is -78~-50 DEG C Under, the reaction was continued 2-4h, after having reacted, the reaction solution of gained after filtering, tie again after vacuum distillation removes solvent by filtrate Crystalline substance obtains double fluorine sulfonamide lithium salts.
Wherein, the mass ratio of the dosage of the resin lithium and double fluorine sulphonyl ammonia is 1~5：1, it is preferably 3~5：1.
Wherein, the resin lithium described in step C is using resin as the resin lithium salts containing lithium ion of Material synthesis, is existing Have, preferably such as formula (5), (6) (7) or the resin lithium shown in (8),
Wherein, above-mentioned resin lithium is prepared using following methods：Contain N- methyl-iV-benzyl second into repetitive unit Solvent organic amine and deacetylation reagent are added in the resin of amide, under microwave irradiation, resin amine is made；Then to institute Organic solvent is added in the resin amine obtained, resin lithium salts is obtained by the reaction with highly basic containing lithium；Wherein, deacetylation examination Agent is tetrabutyl ammonium fluoride, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, ammonium iodide, ammonium fluoride, ammonium bromide Or ammonium chloride；
The resin is with one of lower structure：
The reaction equation of resins synthesis shown in formula (1) correspondingly resin lithium is as shown in formula I：
The reaction equation of resins synthesis shown in formula (2) correspondingly resin lithium is as shown in formula II：
The reaction equation of resins synthesis shown in formula (3) correspondingly resin lithium is as shown in formula III：
The reaction equation of resins synthesis shown in formula (4) correspondingly resin lithium is as shown in formula IV：
The specific preparation process of above-mentioned resin lithium is to be added to resin and solvent organic amine and deacetylation reagent Among sealed glass tube, under the microwave irradiation of 250-300W, 50-80 DEG C is warming up to, reacts 5-60min, gained reaction solution After filtering, washed successively through acid solution, aqueous slkali and water, be dried to obtain resin amine；It is added in into the resin amine of gained After being cooled to -78~-50 DEG C, highly basic containing lithium is slowly added dropwise in organic solvent thereto, and rate of addition is 1~5mL/min, entirely - 78~-50 DEG C, after being added dropwise are maintained the temperature at during being added dropwise, under conditions of temperature is kept as -78~-50 DEG C, is continued After reacting 2-4h, after having reacted, after filtering, filtrate is molten through vacuum distillation removing at -78~-50 DEG C for the reaction solution of gained After agent, double fluorine sulfonamide lithium salts are recrystallized to give.
Wherein, the highly basic containing lithium be butyl lithium, isobutyl group lithium, tert-butyl lithium, lithium amide, lithium hydride, diisopropyl Ammonia lithium or lithium metal.
The dosage of the deacetylation reagent and the mass ratio of resin are 0.8~1.5：1, preferably 0.8~ 1.3：1, further preferably 1~1.1：1；The organic amine is selected from methyl amine, base amine, propyl amine, methanediamine, base Diamines or propyl diamine, the dosage of organic amine and the mass ratio of resin are 4~6：1, it is preferably 5~5.5：1；
During preparing resin amine by resin, reaction temperature is preferably controlled to 70 DEG C~80 DEG C.
Reaction temperature is preferably controlled to -78~-75 DEG C during preparing resin lithium by resin amine.
The organic solvent is selected from dichloromethane, chloroform, tetrahydrofuran, toluene, methanol, ethyl alcohol, one kind in ether Or the mixture of two kinds of arbitrary proportions, the organic solvent described in above steps can be it is same, can not also be same, step In A, the organic solvent is preferably dichloromethane, chloroform, tetrahydrofuran, a kind of in toluene or two kinds of arbitrary proportions mixed Close object, further preferably chloromethanes, chloroform or toluene, the molar ratio of the dosage of organic solvent and the fragrant methyl amine as shown in I Preferably 5~15：1, further preferably 10~15：1；Organic solvent described in step B is preferably methanol, ethyl alcohol and tetrahydrochysene A kind of or two kinds of arbitrary proportions mixture in furans；In step C, the organic solvent is preferably ether or tetrahydrofuran； The matter that described organic solvent during resin lithium is preferably ether or tetrahydrofuran, dosage and resin is prepared by resin amine Amount is than being preferably 20~50：1, further preferably 40~50：1.
Advantageous effect：This method raw material is cheap and easy to get, and reaction step is simple, and yield is high, almost pollution-free, without unkind danger Reaction condition, product are easily purified, and are suitable for domestic mass production.
Specific embodiment
In order to deepen the understanding of the present invention, below in conjunction with embodiment, the invention will be further described, the embodiment It is only used for explaining the present invention, be not intended to limit the scope of the present invention..
Embodiment 1
1) resins of the 10g as shown in following formula (1), 10g ammonium bromides are weighed, 40g ethylenediamines are added among sealed glass tube, Temperature rises to 80 DEG C of reaction 1h under microwave irradiation, and after completion of the reaction, temperature is cooled to room temperature filtering to band, with 400mL 1M HCL Solution is washed, and is washed with 400mL 1M NaOH solutions, is finally washed with water 500mL again again, dry to collect admittedly Body obtains 5.3g resin amine.
2) 250mL tetrahydrofurans are added in into the 5.3g resin amine obtained by step 1), are then added in there-necked flask, temperature Tert-butyl lithium 5.3mL, rate of addition 1.76mL/min is slowly added dropwise after being down to -78 DEG C, process is entirely added dropwise, keeps temperature For -78 DEG C~-75 DEG C, after being added dropwise, temperature is being kept to be -78 DEG C~-75 DEG C, the reaction was continued 1h, is waiting to have reacted Bi Hou, fast direct take over filter, after with 50mL tetrahydrofurans (- 78 DEG C~-75 DEG C), much filtrate is washed three times, the filter collected Go out object, be resin lithium, amount to 4.2g, yield is disregarded.
Resins synthesis shown in formula (1) is correspondingly shown in the reaction equation following formula of resin lithium：
Embodiment 2
1) resins of the 10g as shown in following formula (2), 15g ammonium bromides are weighed, 50g ethylenediamines are added among sealed glass tube, Temperature rises to 80 DEG C of reaction 1h under microwave irradiation, and after completion of the reaction, temperature is cooled to room temperature filtering to band, with 400mL 1M HCL Solution is washed, and is washed with 400mL 1M NaOH solutions, is finally washed with water 400mL again again, dry to collect admittedly Body obtains 5.1g resin amine.
2) 250mL tetrahydrofurans are added in into the 5.1g resin amine of gained, are added in there-necked flask, temperature is down to -78 DEG C Tert-butyl lithium 5.3mL, rate of addition 1.76mL/min are slowly added dropwise afterwards, process is entirely added dropwise, it is -78 DEG C to keep temperature ~-75 DEG C, after being added dropwise, temperature is being kept to be -78 DEG C~-75 DEG C, the reaction was continued 1h, is being treated after completion of the reaction, soon Speed directly filtering, after with 50mL tetrahydrofurans (- 78 DEG C~-75 DEG C), much filtrate is washed three times, the much filtrate collected, i.e., For resin lithium salts, amount to 4.0g, yield is disregarded.
The reaction equation of resins synthesis shown in formula (2) correspondingly resin lithium is shown below：
Embodiment 3
1) resins of the 10g as shown in following formula (3), 9g ammonium bromides are weighed, 60g ethylenediamines are added among sealed glass tube, Temperature rises to 80 DEG C of reaction 1h under microwave irradiation, and after completion of the reaction, temperature is cooled to room temperature filtering to band, with 400mL 1M HCL Solution is washed, and is washed with 450mL 1M NaOH solutions, is finally washed with water 500mL again again, dry to collect admittedly Body obtains 5.5g resin amine.
2) 250mL tetrahydrofurans are added in into the 5.1g resin amine obtained by step 1), are added in there-necked flask, temperature is down to Tert-butyl lithium 5.8mL, rate of addition 1.76mL/min is slowly added dropwise after -78 DEG C, process is entirely added dropwise, keep temperature for - 78 DEG C~-75 DEG C, after being added dropwise, temperature is being kept to be -78 DEG C~-75 DEG C, the reaction was continued 1h, is treating that reaction finishing Afterwards, fast direct takes over filter, and after with 50mL tetrahydrofurans (- 78 DEG C~-75 DEG C), much filtrate is washed three times, that collects filters out Object is resin amine, amounts to 4.1g, and yield is disregarded.
The reaction equation of resins synthesis shown in formula (3) correspondingly resin lithium is shown below：
Embodiment 4
1) resins of the 10g as shown in following formula (4), 12g ammonium bromides are weighed, 40g ethylenediamines are added among sealed glass tube, Temperature rises to 80 DEG C of reaction 1h under microwave irradiation, and after completion of the reaction, temperature is cooled to room temperature filtering to band, with 400mL 1M HCL Solution is washed, and is washed with 400mL 1M NaOH solutions, is finally washed with water 400mL again again, dry to collect admittedly Body obtains 5.0g resin amine.
2) 250mL tetrahydrofurans are added in into the 5.0g resin amine obtained by step 1), are added in there-necked flask, temperature is down to Tert-butyl lithium 5.3mL, rate of addition 1.76mL/min is slowly added dropwise after -78 DEG C, process is entirely added dropwise, keep temperature for - 78 DEG C~-75 DEG C, after being added dropwise, temperature is being kept to be -78 DEG C~-75 DEG C, the reaction was continued 1h, is treating that reaction finishing Afterwards, fast direct takes over filter, and after with 50mL tetrahydrofurans (- 78 DEG C~-75 DEG C), much filtrate is washed three times, that collects filters out Object is resin lithium, amounts to 4.4g, and yield is disregarded.
The reaction equation of resins synthesis shown in formula (4) correspondingly resin lithium is shown below：
If the resin of formula (1) (2) (3) and (4) is existing in embodiment 1-4, buy in South Korea KUKDO ChemicaL or South Korea KANGNAM Chem.
Embodiment 5
1) 10.7g benzene methanamines are weighed, after 8.13mL triethylamines are dissolved in chloroform 800mL, are added to constant pressure funnel In the there-necked flask of thermometer, chlorine fluorine sulphonyl 18.22mL, time for adding 1h is slowly added dropwise after being down to 0 DEG C in temperature, entire to drip Reaction temperature is added to be maintained at 0 DEG C~5 DEG C, 35 DEG C are warming up to after being added dropwise, the reaction was continued 4h, band after completion of the reaction, by gained Reaction solution be filtered, be collected into filtrate after vacuum distillation removes chloroform, add in after 1h is stirred at room temperature in ether 500mL, It filters again, is collected into filtrate after vacuum distillation removes ether, add in normal hexane 50mL and be recrystallized to give 26.54g benzyls Double fluorine sulfonamide, yield 98%, in terms of benzene methanamine.
2) the double fluorine sulfonamide of 26.54g benzyls are weighed and are dissolved in 800mL tetrahydrofurans/ethyl alcohol (volume ratio 1：1) after in, It is added among hydrogen reaction kettle, adds in 0.94g palladiums/carbon (mass fraction of palladium is 10%) catalyst, slowly led with ready Enter hydrogen, pressure is controlled in 20psi, and temperature is slowly adjusted every 1h to 40 DEG C, reaction time 10h from 25 DEG C, and band has reacted Bi Wendu is cooled to room temperature, and is directly filtered, and much filtrate is washed three times with 50mL tetrahydrofurans, metallic catalyst is recycled, Collection obtains filtrate after vacuum distillation, adds in normal hexane 50mL and is recrystallized to give the double fluorine sulfonamide of 15.77g, yield 89%, In terms of the double fluorine sulfonamide of benzyl.
3) the double fluorine sulfonamide of 15.77g are weighed it is dissolved in tetrahydrofuran 500mL and form double fluorine sulfonamide solutions, weighs 22g implementations Resin lithium prepared by 1 is dissolved in tetrahydrofuran 20mL formation resin lithium solution and is added in there-necked flask, its temperature is down to -78 After DEG C, double fluorine sulfonamide solutions, time for adding 1h are slowly added dropwise thereto, entire drip reacting temperature is maintained at -78 DEG C ~-75 DEG C, -78 DEG C~-75 DEG C the reaction was continued 2h, treat after completion of the reaction, to treat after completion of the reaction after being added dropwise, entire to post-process Process uses after -78 DEG C~-75 DEG C carry out and solvent for use is cooled to -78 DEG C~-75 DEG C, specific process For：Fast direct connects filtering reacting liquid, and much filtrate is washed three times with 50mL tetrahydrofurans, to recycle excessive resin lithium；It collects To filtrate after vacuum distillation removes solvent, after 1h is stirred at room temperature in addition ether 200mL, the solid being obtained by filtration is through 50mL second After ether washing three times, double fluorine sulfonamide lithium salts 12.8g are obtained, yield is disregarded.
Specific reaction equation is shown below：
Embodiment 6
1) 10.7g benzene methanamines are weighed to be dissolved among 800mL toluene, add in three mouthfuls with constant pressure funnel and thermometer In bottle, 5.3mL fluosulfonic acid is slowly added dropwise at 25 DEG C, time for adding is 30 minutes, and 110 DEG C are warming up to after being added dropwise, and is continued 8h is reacted, band reaction finishes temperature and is down to room temperature, and 100mL saturated solution of sodium carbonate and 500mL distilled water is added to be extracted, is received Collect organic phase, magnesium sulfate is added in into the organic phase of collection, it is dried, filtered, the filtrate of collection removes through vacuum distillation After solvent, add in normal hexane 50mL and be recrystallized to give the double fluorine sulfonamide of 24.57g benzyls, yield (in terms of benzene methanamine) is 91%.
2) mixture (the two volume that the double fluorine sulfonamide of 24.57g benzyls are dissolved in 8000mL tetrahydrofurans and ethyl alcohol is weighed Than 1：1) in, it is added among hydrogen reaction kettle, adds in 0.87g palladiums/carbon (mass fraction of palladium is 10%) catalyst, band prepares It finishes and slowly imports hydrogen, for the control of general pressure in 20psi, temperature is adjusted up 3 DEG C to 40 DEG C from 25 DEG C every 1h, during reaction Between for 10h, band reaction finishes temperature and is cooled to room temperature, and filters, and much filtrate washs it three times with 50mL tetrahydrofurans, recycles metal Catalyst, filtrate add in normal hexane 50mL and are recrystallized to give the double fluorine sulfonamide of 13.7g, yield is (with benzyl after vacuum distillation Double fluorine sulfonamide meters) it is 84%.
3) the double fluorine sulfonamide of 13.7g are weighed it is dissolved in tetrahydrofuran 500mL and form double fluorine sulfonamide solutions, weighs 20g implementations Resin lithium prepared by example 2 is dissolved in tetrahydrofuran 20mL formation resin lithium solution and adds in into there-necked flask, is slowly added dropwise thereto Double fluorine sulfonamide solutions, time for adding 1h, entire drip reacting temperature is maintained at -78~-75 DEG C, after being added dropwise, -78 The reaction was continued at~-75 DEG C 2h, treats after completion of the reaction, to treat after completion of the reaction, entire last handling process is in -78 DEG C~-75 DEG C feelings Progress and solvent for use use after being cooled to -78 DEG C~-75 DEG C under condition, and specific process is：Fast direct connects filtering reacting liquid, Much filtrate is washed three times with 50mL tetrahydrofurans, to recycle excessive resin lithium；It is molten through vacuum distillation removing to be collected into filtrate After agent, after 1h is stirred at room temperature in addition 200mL ether, the solid being obtained by filtration obtains double fluorine sulphurs after the washing three times of 50mL ether Amide lithium salts 11.3g, yield are disregarded.
Specific reaction equation is shown below：
Embodiment 7
1) 13.5g 3 is weighed, 5- dimethyl-benzyl amines after 41.7mL triethylamines are dissolved in chloroform 800mL, are added to persevering In the there-necked flask for pressing dropping funel and thermometer, chlorine fluorine sulphonyl 18.27mL, time for adding is slowly added dropwise after being down to 0 DEG C in temperature For 1h, entire drip reacting temperature is maintained at 0 DEG C -5 DEG C, and 35 DEG C are warming up to after being added dropwise, the reaction was continued 4h, and band reaction finishes Afterwards, directly filter, be collected into filtrate after vacuum distillation removing chloroform, after 1h is stirred at room temperature in addition ether 500mL, mistake Filter, collection obtain filtrate after vacuum distillation removes ether, add in normal hexane 50mL and are recrystallized to give 27.8g 3,5- dimethyl The double fluorine sulfonamide of benzyl, yield (in terms of benzene methanamine) are 93%.
2) 27.8g 3 is weighed, the double fluorine sulfonamide of 5- dimethyl benzyls are dissolved in the mixing of 8000mL tetrahydrofurans and ethyl alcohol Object (the two volume ratio 1：1) after in, it is added among hydrogen reaction kettle, adds in 0.92g palladiums/carbon (mass fraction of palladium is 10%), With ready slow importing hydrogen, in 20psi, temperature is slowly adjusted every 1h to 40 DEG C from 25 DEG C for pressure control, during reaction Between for 10h, band reaction finishes temperature and is cooled to room temperature, and filters, and much filtrate wash three times with 50mL tetrahydrofurans, recycles metal and urges Agent, filtrate add in normal hexane 50mL and are recrystallized to give the double fluorine sulfonamide of 12.45g, yield after vacuum distillation removes solvent (with the double fluorine sulfonamide meters of 3,5- dimethyl benzyls) is 72%.
3) the double fluorine sulfonamide of 12.45g are weighed it is dissolved in tetrahydrofuran 500mL and form double fluorine sulfonamide solutions, weighs 13.6g realities It applies the resin lithium prepared by 3 and is dissolved in tetrahydrofuran 20mL and forms resin lithium solution and be added in there-necked flask, its temperature is down to- After 78 DEG C, double fluorine sulfonamide solutions, time for adding 1h are slowly added dropwise thereto, entire drip reacting temperature is maintained at -78 ~-75 DEG C, -78~-75 DEG C of the reaction was continued 2h, band after completion of the reaction, are treated after completion of the reaction, entirely to post-process after being added dropwise Journey uses after -78 DEG C~-75 DEG C carry out and solvent for use is cooled to -78 DEG C~-75 DEG C, and specific process is： Fast direct connects filtering reacting liquid, and much filtrate is washed three times with 50mL tetrahydrofurans, to recycle excessive resin lithium；It is collected into filter Liquid is after vacuum distillation removes solvent, and after 1h is stirred at room temperature in addition 200mL ether, the solid being obtained by filtration is washed through 50mL ether After three times, it is collected into mother liquor and obtains the double fluorine sulfonamide lithium salts of 10.5g, yield (in terms of double fluorine sulfonamide) 82% through vacuum distillation.
Specific reaction equation is shown below：
Embodiment 8
Same as Example 5, the difference is that in step 5), used resin lithium is the resin lithium described in embodiment 4, is passed through After collection, the double fluorine sulfonamide lithium salts of 10.6g benzyls are obtained, yield is disregarded.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention With within principle, any modifications, equivalent replacements and improvements are made should all be included in the protection scope of the present invention god.

Claims (9)

  1. A kind of 1. method for preparing imidodisulfuryl fluoride lithium salt using fragrant methyl amine, which is characterized in that comprise the following steps：
    Fragrant methyl amines of the A shown in by formula I is dissolved in organic solvent, is carried out sulfuryl amine reaction with fluosulfonic acid or chlorine fluorine sulphonyl, is obtained To the double fluorine sulfonamide of fragrant methyl shown in formula II；
    The double fluorine sulfonamide of fragrant methyl that step A is obtained shown in formula II by B are dissolved in organic solvent, under catalyst action, warp Hydrogen reducing obtains double fluorine sulphonyl ammonia；
    The obtained double fluorine sulphonyl ammonia of step B and resin lithium are dissolved in organic solvent by C respectively, are carried out ion exchange and are finally produced Object imidodisulfuryl fluoride lithium salt；
    R1=H, CH3,CH3CH2,
    R2=H, CH3,CH3CH2,
    Wherein, the resin lithium described in step C is prepared using following methods：Contain N- methyl-N- benzene into repetitive unit Solvent organic amine and deacetylation reagent are added in the resin of methylacetamide, under microwave irradiation, resin amine is made；So Organic solvent is added in the resin amine of backward gained, resin lithium salts is obtained by the reaction with highly basic containing lithium；Wherein, it is described deacetylated Reaction reagent is tetrabutyl ammonium fluoride, tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium iodide, ammonium iodide, ammonium fluoride, Ammonium bromide or ammonium chloride；
    The resin is with one of lower structure：
  2. 2. a kind of method for preparing imidodisulfuryl fluoride lithium salt using fragrant methyl amine is required according to claim 1, It is characterized in that, the fragrant methyl amine shown in formula I carries out the catalyst of sulfuryl amine reaction as basic catalyst with chlorine fluorine sulphonyl, described Basic catalyst for triethylamine, diisopropylethylamine, pyridine, sodium hydroxide, potassium hydroxide, sodium hydride, hydrofining, tertiary butyl Sodium oxide molybdena or tertiary butyl potassium oxide.
  3. 3. a kind of method for preparing imidodisulfuryl fluoride lithium salt using fragrant methyl amine according to claim 2, feature It is, the detailed process that fragrant methyl amine shown in formula I carries out sulfuryl amine reaction with chlorine fluorine sulphonyl is by fragrant methyl amine shown in formula I It is dissolved in basic catalyst in organic solvent, after being cooled to 0~10 DEG C, chlorine fluorine sulphonyl is added dropwise thereto, during entire dropwise addition It is 0~10 DEG C to keep reaction temperature, and 20~35 DEG C are warming up to after being added dropwise, the reaction was continued 4~8h, after reaction, reaction Solution is filtered, and filtrate adds in ether precipitation, filter again, the filtrate of collection is through subtracting after vacuum distillation removes organic solvent After ether is distilled off in pressure, the double fluorine sulfonamide of fragrant methyl through being recrystallized to give shown in formula II.
  4. 4. a kind of method for preparing imidodisulfuryl fluoride lithium salt using fragrant methyl amine according to claim 1, feature It is, the detailed process that fragrant methyl amine shown in formula I carries out sulfuryl amine reaction with fluosulfonic acid is that fragrant methyl amine shown in formula I is molten In organic solvent, fluosulfonic acid is slowly added dropwise thereto, entire be added dropwise keeps reaction temperature to be added dropwise for 20~40 DEG C in the process After be warming up to 100~120 DEG C, the reaction was continued 8~for 24 hours, and after reaction, reaction solution collects organic phase through extraction, collection Organic phase is recrystallized to give the double fluorine sulphonyl of fragrant methyl shown in formula II after dry water removal, vacuum distillation remove organic solvent Amine.
  5. 5. a kind of method for preparing imidodisulfuryl fluoride lithium salt using fragrant methyl amine according to claim 1, feature It is, the molar ratio of the dosage of the fluosulfonic acid or chlorine fluorine sulphonyl and the fragrant methyl amine as shown in I is 2.0~2.5：1.
  6. 6. a kind of method for preparing imidodisulfuryl fluoride lithium salt using fragrant methyl amine according to claim 1, feature It is, in step B, it is 5~25psi to be passed through hydrogen to pressure.
  7. 7. a kind of method for preparing imidodisulfuryl fluoride lithium salt using fragrant methyl amine according to claim 1, feature It is, the detailed process of step C forms double fluorine sulfonamide for double fluorine sulfonamide and resin lithium are dissolved in respectively in anhydrous solvent After resin lithium solution is cooled to -78~-50 DEG C, double fluorine sulfonamide solutions are slowly added dropwise in solution and resin lithium solution thereto, The entire process that is added dropwise keeps reaction warm for -78~-50 DEG C, after being added dropwise, in the case where keeping temperature as -78~-50 DEG C, The reaction was continued 2~4h, after having reacted, the reaction solution of gained after filtering, at -78~-50 DEG C through vacuum distillation remove by filtrate After removing solvent, double fluorine sulfonamide lithium salts are recrystallized to give.
  8. 8. a kind of method for preparing imidodisulfuryl fluoride lithium salt using fragrant methyl amine according to claim 1, feature It is, the specific preparation process of resin lithium is that resin and solvent organic amine and deacetylation reagent are added to seal glass Among pipe, under the microwave irradiation of 250-300W, be warming up to 50-80 DEG C, react 5-60min, gained reaction solution after filtering, It is washed successively through acid solution, aqueous slkali and water, is dried to obtain resin amine；Organic solvent is added in into the resin amine of gained, After being cooled to -78~-50 DEG C, highly basic containing lithium is slowly added dropwise thereto, rate of addition is 4~5mL/min, during entire dropwise addition - 78~-50 DEG C, after being added dropwise are maintained the temperature at, is keeping temperature as under conditions of -78~-50 DEG C, the reaction was continued 2-4h Afterwards, resin amine lithium is obtained after washing through filtering after the reaction solution of gained.
  9. 9. a kind of method for preparing imidodisulfuryl fluoride lithium salt using fragrant methyl amine according to claim 1, feature It is, the highly basic containing lithium is butyl lithium, isobutyl group lithium, tert-butyl lithium, lithium amide, lithium hydride, diisopropyl ammonia lithium or gold Belong to lithium.
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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
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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
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