CN105923614B - A kind of method that imidodisulfuryl fluoride lithium salt is prepared using phthalimide - Google Patents

A kind of method that imidodisulfuryl fluoride lithium salt is prepared using phthalimide Download PDF

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CN105923614B
CN105923614B CN201610287182.4A CN201610287182A CN105923614B CN 105923614 B CN105923614 B CN 105923614B CN 201610287182 A CN201610287182 A CN 201610287182A CN 105923614 B CN105923614 B CN 105923614B
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fluorine
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sulfimides
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CN105923614A (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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    • 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
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    • C08F8/00—Chemical modification by after-treatment
    • C08F8/44—Preparation of metal salts or ammonium salts

Abstract

The invention discloses a kind of preparation method of imidodisulfuryl fluoride lithium salt; comprise the following steps, phthalimide is dissolved in organic solvent, sulfuryl amine reaction is carried out with chlorine fluorine sulphonyl or fluorosulfuric acid; O-phthalic fluorine sulfonamide is obtained, its fluorine sulphonyl secondary amine through being reduced to shown in formula iii；Resulting fluorine sulphonyl secondary amine; under acid or alkalescence condition; its fluorine sulphonyl one-level amino acid salt or fluorine sulfonamide through being reduced to shown in iv; it carries out sulfuryl amine reaction with chlorine fluorine sulphonyl or fluorosulfuric acid; double fluorine sulfimides are obtained, then carries out ion exchange with resin lithium and obtains final product fluorine sulfonamide lithium salts；This method raw material is cheap and easy to get, and reactions steps are simple, and yield is high, and almost pollution-free, without unkind and dangerous reaction condition, product is easily purified, and is suitable for domestic a large amount of productionizations.

Description

A kind of method that imidodisulfuryl fluoride lithium salt is prepared using phthalimide
Technical field
The invention belongs to lithium ion battery electrolyte technical field, more particularly to one kind to be prepared using phthalimide The method of imidodisulfuryl fluoride lithium salt.
Background technology
Double fluorine sulfimide lithium (LiN (SO2F)2, hereinafter referred to as LiFSI) and it is an electrolyte with wide application prospect Material, LiFSI conductance is suitable, and heat endurance, electrochemical stability are high；Generation side reaction probability is small, will not produce HF It is indispensable new and high technology class product in current electrolyte of lithium-ion secondary battery Deng corrosive gas.With lithium electricity row The continuous development of industry, its market demand will be increasing, it is possible to star's product supplemented by growth in salt lithium salt compound.
The conventional synthetic method of double fluorine sulphonyl ammonia lithium salts is mainly with the source of ammoniacal liquor, ammonium salt or ammonia as ammonia, thereafter Add chlorine fluorine sulphonyl or fluorosulfuric acid etc. and synthesize dichlorphenamidum, then carry out double fluorine sulphonyl ammonia lithiums obtained by fluorination and lithiation Salt, such method have some following shortcoming：1) during industrial mass production, the correct amount of ammonia is it is difficult to which that shapes is excessive Very few to promote to generate unnecessary accessory substance, 2) it is a large amount of when using ammonia, it is easy to set off an explosion at different temperatures and pressures So that safety problem is hidden danger always.
The content of the invention
The invention provides a kind of method that imidodisulfuryl fluoride lithium salt is prepared using phthalimide, this method are former To expect cheap and easy to get, reactions steps are simple, and yield is high, and almost pollution-free, without unkind and dangerous reaction condition, product is easily purified, It is suitable for domestic a large amount of productionizations.
In order to solve the above problems, the technical solution adopted in the present invention is such, and one kind is sub- using phthalyl The method that amine prepares imidodisulfuryl fluoride lithium salt, comprises the following steps：
Phthalimide shown in formula I is dissolved in organic solvent by A, and sulfonamide is carried out with chlorine fluorine sulphonyl or fluorosulfuric acid Reaction, obtains the O-phthalic fluorine sulfonamide shown in formula II；
O-phthalic fluorine sulfonamide shown in formula II obtained by step A is dissolved in organic solvent by B, adds reducing agent, warp After reduction, the 2- methylol benzoyl fluoride sulfimides shown in formula iii are obtained；
2- methylol benzoyl fluoride sulfimides shown in the formula iii that C obtains step B, under the conditions of organic solvent, with acid Property reagent reacting obtains the fluorine sulfanilic shown in iv, or reacts with alkaline reagent to obtain fluorine sulfonamide；
The fluorine sulfanilic or fluorine sulfonamide that step C is obtained are dissolved in organic solvent by D, with chlorine fluorine sulphonyl or fluorosulfuric acid Sulfuryl amine reaction is carried out, obtains double fluorine sulfimides shown in v；
Double fluorine sulfimides that E obtains step D are dissolved in organic solvent to be obtained finally with resin lithium progress ion exchange Product imidodisulfuryl fluoride lithium salt；
X=HCL, H2SO4,H3PO4,MeSO3H,HNO3,4-PhCH3SO3H,HBO3
Chlorine fluorine sulfimide lithium salts prepares specific reaction equation as shown in following formula I or formula II；
Or
In step A and D, phthalimide and chlorine fluorine sulphonyl shown in formula I, or the 2- methylol benzoyls shown in iii Fluorine sulfimide and chlorine fluorine sulphonyl carry out the alkaline reagent that sulfuryl amine reaction is added can be it is same, can also be different, it is excellent Elect triethylamine as, diisopropylethylamine, pyridine, sodium hydroxide, potassium hydroxide, lithium hydroxide, potassium carbonate, sodium carbonate, potassium phosphate, Sodium phosphate or sodium hydride.
In step A, the detailed process of phthalimide and chlorine fluorine sulphonyl progress sulfuryl amine reaction shown in formula I is will Phthalimide is dissolved in organic solvent, adds alkaline reagent, and after being cooled to -20~-10 DEG C, chlorine fluorine sulphur is added dropwise thereto Acyl, it is -20~-10 DEG C that reaction temperature is kept during whole dropwise addition, and 20~35 DEG C are warming up to after being added dropwise, continues reaction 12 ~24h, for the reaction solution of gained after vacuum distillation removing is organic, organic phase is collected in extraction, then organic through being evaporated under reduced pressure removing Solvent obtains the O-phthalic fluorine sulfonamide shown in formula ii；
The dosage of described alkaline reagent and the mol ratio of phthalimide shown in formula i are 1.2~2.4：1.
The detailed process that phthalimide shown in formula I carries out sulfuryl amine reaction with fluorosulfuric acid is by phthalyl Imines is dissolved in organic solvent, and after being cooled to -20~-10 DEG C, fluorosulfuric acid is added dropwise thereto, and reaction is kept during whole dropwise addition Temperature is -20~-10 DEG C, and 20~35 DEG C are warming up to after being added dropwise, and continues 12~24h of reaction, and the reaction solution of gained adds Distilled water is extracted, and organic phase is collected in extraction, then obtains the O-phthalic shown in formula ii through being evaporated under reduced pressure removing organic solvent Fluorine sulfonamide.
In step A, dosage and the phthalimide mol ratio shown in formula I of described chlorine fluorine sulphonyl or fluorosulfuric acid are 1.2~2.4：1；
Step B detailed process is cooled to -5 for the O-phthalic fluorine sulfonamide shown in formula ii is dissolved in organic solution After~0 DEG C, reducing agent is added thereto, it is -5~0 DEG C that reaction temperature is kept in whole process, it is warming up to 20 after being added dropwise~ 35 DEG C, continuing 24~30h of reaction, for the reaction solution of gained after being evaporated under reduced pressure and removing organic solvent, organic phase is collected in extraction, then The 2- methylol benzoyl fluoride sulfimides shown in formula iii are obtained after being evaporated under reduced pressure and removing organic solvent.
In step B, the dosage of reducing agent is 1.2~1.5 with the mol ratio of O-phthalic fluorine sulfonamide：1.
Step C detailed process drops for the 2- methylol benzoyl fluoride sulfimides shown in formula iii are dissolved in organic solution After extremely -5~0 DEG C of temperature, acid is added thereto, it is -5~0 DEG C that reaction temperature is kept in whole process, and 60 are warming up to after being added dropwise ~80 DEG C, continue 24~30h of reaction, the reaction solution of gained is filtered, washing, dry fluorine sulfanilic.
Step C detailed process drops for the 2- methylol benzoyl fluoride sulfimides shown in formula iii are dissolved in organic solution After extremely -5~0 DEG C of temperature, alkali is added thereto, it is -5~0 DEG C that reaction temperature is kept in whole process, and 60 are warming up to after being added dropwise ~80 DEG C, continue 24~30h of reaction, for the reaction solution of gained after decompression removes organic solvent, organic phase is collected in extraction, is collected Organic phase through dry remove water, be evaporated under reduced pressure remove organic solvent after, obtain fluorine sulfonamide.
In step C, described acid is hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, boric acid, 4- benzyls sulfuric acid or methylsulfuric acid, institute The alkali stated is sodium hydroxide, potassium hydroxide, lithium hydroxide, potassium carbonate, sodium carbonate, potassium phosphate, sodium phosphate or sodium hydride, acid or alkali Dosage and formula iii shown in the mol ratios of 2- methylol benzoyl fluoride sulfimides be 2.5~3.5：1.
In step D, the 2- methylol benzoyl fluoride sulfimides shown in iii carry out the specific of sulfuryl amine reaction with chlorine fluorine sulphonyl 2- methylol benzoyl fluoride sulfimides shown in formula iii is are dissolved in organic solution by process, addition alkaline reagent, be cooled to- After 20~-10 DEG C, chlorine fluorine sulphonyl is slowly added dropwise thereto, it is -20~-10 DEG C that reaction temperature is kept during whole dropwise addition, drop 20~35 DEG C are warming up to after adding, continues 12~24h of reaction, the reaction solution of gained is after being evaporated under reduced pressure and removing solvent, extraction Collection organic phase is taken, then double fluorine sulfimides shown in formula v are obtained after being evaporated under reduced pressure and removing organic solvent；
The detailed process that 2- methylol benzoyl fluoride sulfimides shown in iii carry out sulfuryl amine reaction with fluorosulfuric acid is by formula 2- methylol benzoyl fluoride sulfimides shown in iii are dissolved in organic solution, after being cooled to -20~-10 DEG C, are slowly dripped thereto Add fluorosulfuric acid, it is -20~-10 DEG C that reaction temperature is kept during whole dropwise addition, and 20~35 DEG C are warming up to after being added dropwise, and is continued 12~24h is reacted, the reaction solution of gained is removed in solvent step D through being evaporated under reduced pressure, described chlorine fluorine sulphonyl or fluorosulfuric acid Dosage is 1.2~2.4 with the mol ratio of fluorine sulfanilic or fluorine sulfonamide shown in formula iv：1；The dosage of alkaline reagent and formula iv The mol ratio of shown fluorine sulfanilic or fluorine sulfonamide is 1.2~2.4：1.
Step E detailed process forms double fluorine sulphonyl for double fluorine sulfonamide and resin lithium are dissolved in organic solvent respectively Amine aqueous solution and resin lithium solution, after resin lithium solution is cooled into -5~0 DEG C, double fluorine sulfonamide solutions are slowly added dropwise thereto, The whole process holding reaction temperature that is added dropwise is 0 DEG C~5 DEG C, after being added dropwise, in the case where keeping temperature is 0 DEG C~5 DEG C, and continuation 8~12h is reacted, after having reacted, after filtering, filtrate recrystallizes the reaction solution of gained after being evaporated under reduced pressure and removing solvent To double fluorine sulfonamide lithium salts.
Wherein, the mass ratio of the dosage of described resin lithium and double fluorine sulphonyl ammonia is 1~6：1.
Wherein, the resin lithium described in step E is the resin lithium salts containing lithium ion using resin as Material synthesis, preferably Resin lithium as shown in formula (3) or (4),
Described resin lithium is prepared using following methods：Dense sulphur is added in the resin containing phenyl ring into repeat unit Sour strong reagents, sulfonating reaction is carried out, then reacted with lithium hydroxide or lithium carbonate, resin lithium is made；
Described resin is one of following structure：
Among resin and the concentrated sulfuric acid is are added to sealed glass tube by the specific preparation process of described resin lithium, it is warming up to 30-40 DEG C, 80-100min is reacted, gained reaction solution is cooled to 0-5 DEG C, is slowly added to lithium hydroxide or carbon through supercooling Sour lithium carries out neutralization reaction, after completion of the reaction, the solid organic solvent washing being filtrated to get, is dried to obtain resin lithium salts.
The dosage of the described concentrated sulfuric acid and the mass ratio of resin are 1：1~2, the dosage or carbonic acid of described lithium hydroxide The mass ratio of lithium and resin is 1：3~5.
Described organic solvent is selected from dichloromethane, chloroform, tetrahydrofuran, toluene, methanol, ethanol, one kind in ether Or the mixture of two kinds of arbitrary proportions, the organic solvent used in above steps can be it is same, can also be different.Step In rapid A or D, used organic solvent is preferably dichloromethane, chloroform, tetrahydrofuran, a kind of or two kinds of any ratios in toluene The mixture of example, more preferably dichloromethane, chloroform or tetrahydrofuran, in step B or C, described organic solvent is preferred For methanol, ethanol, propyl alcohol, 1,2- dimethoxy ether, a kind of or two kinds of arbitrary proportions mixture in tetrahydrofuran.
Beneficial effect：This method raw material is cheap and easy to get, and reactions steps are simple, and yield is high, almost pollution-free, without unkind danger Reaction condition, product are easily purified, and are suitable for domestic a large amount of productionizations.
Figure of description
Fig. 1 is the F-NMR collection of illustrative plates for double fluorine sulfonamide that the embodiment of the present invention 16 obtains.
Embodiment
In order to deepen the understanding of the present invention, below in conjunction with embodiment and accompanying drawing, the invention will be further described, should Embodiment is only used for explaining the present invention, is not intended to limit the scope of the present invention..
A kind of preparation method of resin lithium of embodiment 1
1) resins of the 10g as shown in formula (1) is weighed, is added among sealed glass tube, temperature is down to 5 DEG C, is slowly added to Concentrated sulfuric acid 20g, temperature rise to 30-40 DEG C of reaction 1h, and after completion of the reaction, temperature adds lithium hydroxide 20g after being down to 0-5 DEG C and entered band Row neutralization reaction, band after completion of the reaction, filtering, are washed three times with ethanol or methanol, dried, and collection obtains 13.8g resin lithiums, receives Rate is disregarded.
Involved specific reaction equation is shown below in above-mentioned preparation method：
Embodiment 2
Resins of the 10g as shown in formula (2) is weighed, is added among sealed glass tube, temperature is down to 5 DEG C, is slowly added to dense Sulfuric acid 20g, temperature rise to 30-40 DEG C of reaction 1h, and after completion of the reaction, temperature adds in lithium carbonate 10g progress band after being down to 0-5 DEG C And reaction, band after completion of the reaction, filtering, are washed three times with ethanol or methanol, dried, collection obtains 13.1g resin lithium salts, yield Disregard.
Involved specific reaction equation is shown below in above-mentioned preparation method：
Embodiment 3
Weigh 14.7g O-phthalics imines and after triethylamine 19.5mL is dissolved in dichloromethane 150mL, be added to there-necked flask In, chlorine fluorine sulphonyl 8.8mL, time for adding 20min is slowly added dropwise in temperature after being down to -20 DEG C, whole drip reacting temperature is protected Hold at -20 DEG C~-10 DEG C, 35 DEG C are warming up to after being added dropwise, continue to react 12h, question response finishes, and adds 200mL distilled water Extracted, after collecting organic phase, into organic phase, it is dried addition MgSO4, filters, and it is organic molten to be evaporated under reduced pressure removing Agent obtains 22g O-phthalic fluorine sulfonamide, and yield (in terms of O-phthalic imines) is 96%.
Embodiment 4
Weigh 14.7g O-phthalics imines and after diisopropylethylamine 24.3mL is dissolved in dichloromethane 150mL, be added to three In mouth bottle, chlorine fluorine sulphonyl 8.8mL, time for adding 20min, whole dropwise reaction temperature is slowly added dropwise after being down to -20 DEG C in temperature Degree is maintained at -20 DEG C~-10 DEG C, and 35 DEG C are warming up to after being added dropwise, and continues to react 24h, and question response finishes, and adds 200mL and steams Distilled water is extracted, and after collecting organic phase, into organic phase, it is dried addition MgSO4, filters, and being evaporated under reduced pressure removing has Solvent, obtains 21g O-phthalic fluorine sulfonamide, and yield (in terms of O-phthalic imines) is 95%.
Embodiment 5
Weigh after 14.7g O-phthalics Asia is dissolved in dichloromethane 150mL, be added in there-necked flask, temperature be down to -20 DEG C it After be slowly added dropwise fluorosulfuric acid 25.5g, time for adding 20min, whole drip reacting temperature is maintained at -20 DEG C~-10 DEG C, is added dropwise After be warming up to 35 DEG C, continue to react 24h, question response finishes, and adds 200mL distilled water and is extracted, after collecting organic phase, MgSO4 is added into organic phase it is dried, filter, be evaporated under reduced pressure and remove organic solvent, obtain 20g O-phthalic fluorine sulphurs Acid amides, yield (in terms of O-phthalic imines) are 93%.
Embodiment 6
Weigh after 14.7g O-phthalic imines is dissolved in dichloromethane 150mL, be added in there-necked flask, temperature is down to -20 DEG C Fluorosulfuric acid 25.5g, time for adding 20min are slowly added dropwise afterwards, whole drip reacting temperature is maintained at -20 DEG C~-10 DEG C, drop 35 DEG C are warming up to after adding, continues to react 24h, question response finishes, and adds 200mL distilled water and is extracted, collects organic phase Afterwards, MgSO4 is added into organic phase it is dried, filtered, be evaporated under reduced pressure and remove organic solvent, obtain 20g O-phthalics Fluorine sulfonamide, yield (in terms of O-phthalic imines) are 92%.
Embodiment 7
The molten amine of O-phthalic fluorine sulphonyl prepared by 22g embodiments 3 is weighed after 400mL methanol, be added to there-necked flask it In, temperature is down to after 0 DEG C, is slowly added to 5.44g sodium borohydrides, and addition finishes, and temperature recovery to 30 DEG C, reaction time is 24h, question response finish vacuum distillation and remove solvent, add 100mL distilled water and are extracted with 100mL dichloromethane, collection has After machine phase, MgSO is added into organic phase4It is dried, filtered, is evaporated under reduced pressure and removes organic solvent, obtain 21.5g 2- Methylol benzoyl fluoride sulfimide, yield (in terms of O-phthalic fluorine sulfonamide) are 96%.
Embodiment 8
Weigh after the O-phthalic fluorine sulfonamide prepared by 22g embodiments 3 is dissolved in 400mL ethanol, be added to there-necked flask it In, temperature is down to after 0 DEG C, be slowly added to 5.1g lithium aluminium hydrides add finish, temperature recovery to 30 DEG C, reaction time 24h, Question response finishes vacuum distillation and removes solvent, adds 100mL distilled water and is extracted with 100mL dichloromethane, collects organic phase Afterwards, MgSO is added into organic phase4It is dried, filtered, is evaporated under reduced pressure and removes organic solvent, obtain 21.7g 2- hydroxyl first Base benzoyl fluoride sulfimide, yield (in terms of O-phthalic fluorine sulfonamide) are 97%.
Embodiment 9
Weigh after the O-phthalic fluorine sulfonamide prepared by 22g embodiments 3 is dissolved in 400mL tetrahydrofurans, be added to three mouthfuls Among bottle, temperature is down to after 0 DEG C, is slowly added to 8.44g lithium aluminium hydrides, and addition finishes, and temperature recovery is to 30 DEG C, the reaction time For 24h, question response finishes vacuum distillation and removes solvent, adds 100mL distilled water and is extracted with 100mL dichloromethane, is collected After organic phase, MgSO is added into organic phase4It is dried, filtered, is evaporated under reduced pressure and removes organic solvent, obtain 21g2- Methylol benzoyl fluoride sulfimide, yield (in terms of O-phthalic fluorine sulfonamide) are 94%.
Embodiment 10
Weigh after the 2- methylol benzoyl fluoride sulfimides prepared by 21g embodiments 7 are dissolved in 350mL tetrahydrofurans, add To among there-necked flask, temperature is down to after 0 DEG C, is slowly added to 32.8g hydrochloric acid solutions (solubility of hydrochloric acid is 35V%), has been added Finish, to 80 DEG C, reaction time 36h, question response finishes temperature and is down to room temperature temperature recovery, and filtering, much filtrate is washed with 5mL methanol Wash three times, be dried to obtain 11.3g fluorine sulfonamide hydrochlorides, yield (in terms of 2- methylol benzoyl fluoride sulfimides) is 93%.
Embodiment 11
Weigh after the 2- methylol benzoyl fluoride sulfimides prepared by 21g embodiments 7 are dissolved in 350mL methanol, be added to three Among mouth bottle, temperature is down to after 0 DEG C, is slowly added to 60.8g phosphoric acid solutions (solubility of phosphoric acid is 50V%), and addition finishes, temperature Degree gos up to 60 DEG C, and reaction time 36h, question response finishes temperature and is down to room temperature, filtering, and much filtrate 5mL methanol washs three times, 16.4g fluorine sulphonyl amine phosphates are dried to obtain, yield (in terms of 2- methylol benzoyl fluoride sulfimides) is 91%.
Embodiment 12
Weigh after the 2- methylol benzoyl fluoride sulfimides prepared by 21g embodiments 8 are dissolved in 350mL ethanol, be added to three Among mouth bottle, temperature is down to after 0 DEG C, is slowly added to 62.8g sulfuric acid solutions (solubility of sulfuric acid is 50V%), and addition finishes, temperature Degree gos up to 80 DEG C, and reaction time 36h, question response finishes temperature and is down to room temperature, filtering, and much filtrate 5mL ethanol washs three times, 16.7g fluorine sulfonamide sulfate is dried to obtain, yield (in terms of 2- methylol benzoyl fluoride sulfimides) is 94%.
Embodiment 13
Weigh after the 2- methylol benzoyl fluoride sulfimides prepared by 21g embodiments 8 are dissolved in 350mL tetrahydrofurans, add To among there-necked flask, temperature is down to after 0 DEG C, is slowly added to 9.0g sodium hydroxides, and addition finishes, and temperature recovery is to 60 DEG C, instead Be 36h between seasonable, question response, which finishes temperature, is down to reduced pressure at room temperature solvent is distilled off, and adds 100mL distilled water and 100mL dichloros Methane is extracted, and after collecting organic phase, MgSO is added into organic phase4It is dried, filtered, being evaporated under reduced pressure removing has Solvent obtains 7.9g fluorine sulfonamide, and yield (in terms of 2- methylol benzoyl fluoride sulfimides) is 89%.
Embodiment 14
Weigh after the 2- methylol benzoyl fluoride sulfimides prepared by 21g embodiments 9 are dissolved in 350mL ethanol, be added to three Among mouthful bottle, temperature is down to after 0 DEG C, is slowly added to 12.6g potassium hydroxide, and addition finishes, and temperature recovery is to 60 DEG C, during reaction Between be 36h, question response, which finishes temperature, is down to reduced pressure at room temperature solvent is distilled off, and adds 100mL distilled water and 100mL dichloromethane Extracted, after collecting organic phase, into organic phase, it is dried addition MgSO4, filters, and it is organic molten to be evaporated under reduced pressure removing Agent obtains 7.6g fluorine sulfonamide, and yield (in terms of 2- methylol benzoyl fluoride sulfimides) is 86%.
Embodiment 15
Weigh after the 2- methylol benzoyl fluoride sulfimides prepared by 21g embodiments 9 are dissolved in 350mL methanol, be added to three Among mouthful bottle, temperature is down to after 0 DEG C, is slowly added to 5.4g lithium hydroxides, and addition finishes temperature recovery to 60 DEG C, the reaction time For 36h, question response, which finishes temperature, is down to reduced pressure at room temperature solvent is distilled off, and adds 100mL distilled water and enters with 100mL dichloromethane Row extraction, after collecting organic phase, into organic phase, it is dried addition MgSO4, filters, and is evaporated under reduced pressure and removes organic solvent 7.4g fluorine sulfonamide is obtained, yield (in terms of 2- methylol benzoyl fluoride sulfimides) is 87%.
Embodiment 16
Weigh the fluorine sulfonamide prepared by 7.4g embodiments 13 and after triethylamine 12.5mL is dissolved in dichloromethane 200mL, add Enter into there-necked flask, chlorine fluorine sulphonyl 6.5mL, time for adding 20min is slowly added dropwise after being down to -20 DEG C in temperature, whole to be added dropwise Reaction temperature is maintained at -20 DEG C~-10 DEG C, and 35 DEG C are warming up to after being added dropwise, and continues to react 12h, and question response finishes, and adds 200mL distilled water is extracted, and after collecting organic phase, into organic phase, it is dried addition MgSO4, filters, and decompression is steamed Distillation goes organic solvent to obtain the double fluorine sulfonamide of 12.8g, and yield (in terms of fluorine sulfonamide) is 95%.
Obtained double fluorine sulfonamide have been carried out with Enantiomeric excess (F-NMR) analysis, as shown in figure 1,
Detection parameters are as follows：
19F-NMR:σ.-52.10(S,1F)
Embodiment 17
2) weigh the fluorine sulfonamide prepared by 7.4g embodiments 14 and diisopropylethylamine 15.6mL is dissolved in dichloromethane After 200mL, it is added in there-necked flask, chlorine fluorine sulphonyl 6.5mL is slowly added dropwise after being down to -20 DEG C in temperature, and time for adding is 20min, whole drip reacting temperature are maintained at -20 DEG C~-10 DEG C, and 35 DEG C are warming up to after being added dropwise, and continue to react 24h, treat Reaction is finished, and adds 200mL distilled water and is extracted, and after collecting organic phase, into organic phase, addition MgSO4 is done to it It is dry, filtering, it is evaporated under reduced pressure removing organic solvent and obtains the double fluorine sulfonamide of 12.9g, yield (in terms of fluorine sulfonamide) is 96%.
Embodiment 18
Weigh the fluorine sulfonamide sulfate prepared by 14.7g embodiments 11 and triethylamine 12.5mL is dissolved in dichloromethane After 150mL, it is added in there-necked flask, fluorosulfuric acid 13.6g, time for adding 20min is slowly added dropwise after being down to -20 DEG C in temperature, Whole drip reacting temperature is maintained at -20 DEG C~-10 DEG C, and 35 DEG C are warming up to after being added dropwise, and continues to react 24h, question response is complete Finish, add 200mL distilled water and extracted, after collecting organic phase, into organic phase, it is dried addition MgSO4, filters, It is evaporated under reduced pressure removing organic solvent and obtains the double fluorine sulfonamide of 12.8g, yield (in terms of fluorine sulfonamide) is 95%.
Embodiment 19
Weigh the fluorine sulfonamide sulfate prepared by 14.7g embodiments 12 and diisopropylethylamine 15.6mL is dissolved in dichloromethane After alkane 150mL, it is added in there-necked flask, fluorosulfuric acid 13.6g is slowly added dropwise after being down to -20 DEG C in temperature, and time for adding is 20min, whole drip reacting temperature are maintained at -20 DEG C~-10 DEG C, and 35 DEG C are warming up to after being added dropwise, and continue to react 24h, treat Reaction is finished, and adds 200mL distilled water and is extracted, and after collecting organic phase, into organic phase, addition MgSO4 is done to it It is dry, filtering, it is evaporated under reduced pressure removing organic solvent and obtains the double fluorine sulfonamide of 12.5g, yield (in terms of fluorine sulfonamide) is 93%.
Embodiment 20
Double fluorine sulfonamide prepared by 8.7g embodiments 16 are weighed to be dissolved in tetrahydrofuran 500mL to form double fluorine sulfonamide molten Liquid, weigh the resin lithium prepared by 8.7g embodiments 1 and be dissolved in 20mL tetrahydrofurans formation resin lithium solution, be added to there-necked flask In, after its temperature is down into -78 DEG C, double fluorine sulfonamide solutions, time for adding 1h, whole dropwise reaction are slowly added dropwise to it Temperature is maintained at -78 DEG C~-75 DEG C, continues at -78 DEG C~-75 DEG C to react 10h after being added dropwise, band after completion of the reaction, soon The direct filtering reacting liquid of speed, much filtrate is washed three times with 50mL tetrahydrofurans, to reclaim excessive resin lithium；It is collected into filtrate After being evaporated under reduced pressure and removing solvent, after 1h is stirred at room temperature in addition 200mL ether, the solid being filtrated to get washs three through 50mL ether After secondary, the double fluorine sulfonamide lithium salts of 5.2g are obtained, yield (in terms of double fluorine sulfonamide) is 57%.
Embodiment 20
Double fluorine sulfonamide prepared by 4.8g embodiments 16 are weighed to be dissolved in tetrahydrofuran 150mL to form double fluorine sulfonamide molten Liquid, weigh the resin lithium prepared by 4.8g embodiments 2 and be dissolved in 20mL tetrahydrofurans formation resin lithium solution, be added to there-necked flask In, after its temperature is down into -78 DEG C, double fluorine sulfonamide solutions, time for adding 1h, whole dropwise reaction are slowly added dropwise to it Temperature is maintained at -78 DEG C~-75 DEG C, continues at -78 DEG C~-75 DEG C to react 8h after being added dropwise, band after completion of the reaction, quickly Direct filtering reacting liquid, much filtrate is washed three times with 50mL tetrahydrofurans, to reclaim excessive resin lithium；It is collected into filtrate warp It is evaporated under reduced pressure after removing solvent, after 1h is stirred at room temperature in addition 200mL ether, the solid being filtrated to get washs three times through 50mL ether Afterwards, the double fluorine sulfonamide lithium salts of 2.0g are obtained, yield (in terms of double fluorine sulfonamide) is 43%.
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 God any modification, equivalent substitution and improvements made etc., should be included in the scope of the protection with principle.

Claims (8)

  1. A kind of 1. method that imidodisulfuryl fluoride lithium salt is prepared using phthalimide, it is characterised in that including following step Suddenly：
    Phthalimide shown in formula I is dissolved in organic solvent by A, and it is anti-to carry out sulfonamide with chlorine fluorine sulphonyl or fluorosulfuric acid Should, obtain the O-phthalic fluorine sulfonamide shown in formula II；
    O-phthalic fluorine sulfonamide shown in formula II obtained by step A is dissolved in organic solvent by B, adds reducing agent, through reduction Afterwards, the 2- methylol benzoyl fluoride sulfimides shown in formula iii are obtained；
    Step B is obtained the 2- methylol benzoyl fluoride sulfimides shown in formula iii by C, under the conditions of organic solvent, is obtained with acid reaction To the fluorine sulfanilic shown in iv, or react with alkali to obtain fluorine sulfonamide；
    The fluorine sulfanilic or fluorine sulfonamide that step C is obtained are dissolved in organic solvent by D, are carried out with chlorine fluorine sulphonyl or fluorosulfuric acid Sulfuryl amine reaction, obtain double fluorine sulfimides shown in v；
    Double fluorine sulfimides that E obtains step D are dissolved in organic solvent obtains final product with resin lithium progress ion exchange Imidodisulfuryl fluoride lithium salt；
    X=HCL, H2SO4,H3PO4,MeSO3H,HNO3,4-PhCH3SO3H, HBO3；
    Described resin lithium is prepared using following methods：It is strong that the concentrated sulfuric acid is added in the resin containing phenyl ring into repeat unit Acid reagent, sulfonating reaction is carried out, then reacted with lithium hydroxide or lithium carbonate, resin lithium is made；
    Described resin is one of following structure：
  2. 2. a kind of method that imidodisulfuryl fluoride lithium salt is prepared using phthalimide according to claim 1, its It is characterised by, the detailed process that the phthalimide shown in formula I carries out sulfuryl amine reaction with chlorine fluorine sulphonyl is by adjacent benzene two Carboximide is dissolved in organic solvent, adds alkaline reagent, and after being cooled to -20~-10 DEG C, chlorine fluorine sulphonyl is added dropwise thereto, whole During individual dropwise addition keep reaction temperature be -20~-10 DEG C, 20~35 DEG C are warming up to after being added dropwise, continue reaction 12~ 24h, the reaction solution of gained add distilled water and extracted, and organic phase is collected in extraction, then removes organic solvent through being evaporated under reduced pressure Obtain the O-phthalic fluorine sulfonamide shown in formula ii；Phthalimide shown in formula I carries out sulfuryl amine reaction with fluorosulfuric acid Detailed process for phthalimide is dissolved in organic solvent, after being cooled to -20~-10 DEG C, fluorine sulphur is added dropwise thereto Acid, it is -20~-10 DEG C that reaction temperature is kept during whole dropwise addition, and 20~35 DEG C are warming up to after being added dropwise, continues reaction 12 ~24h, the reaction solution of gained add distilled water and extracted, and organic phase is collected in extraction, then organic molten through being evaporated under reduced pressure removing Agent obtains the O-phthalic fluorine sulfonamide shown in formula ii.
  3. 3. a kind of method that imidodisulfuryl fluoride lithium salt is prepared using phthalimide according to claim 1, its Be characterised by, step B detailed process for the O-phthalic fluorine sulfonamide shown in ii is dissolved in organic solution, be cooled to -5~ After 0 DEG C, reducing agent is added thereto, it is -5~0 DEG C that reaction temperature is kept in whole process, and 20~35 are warming up to after being added dropwise DEG C, continuing 24~30h of reaction, for the reaction solution of gained after being evaporated under reduced pressure and removing solvent, organic phase is collected in extraction, then through decompression The 2- methylol benzoyl fluoride sulfimides shown in formula iii are obtained after organic solvent is distilled off.
  4. 4. a kind of method that imidodisulfuryl fluoride lithium salt is prepared using phthalimide according to claim 1, its It is characterised by, step C detailed process is that the 2- methylol benzoyl fluoride sulfimides shown in formula iii are dissolved in organic solution, After being cooled to -5~0 DEG C, acid is added thereto, it is -5~0 DEG C that reaction temperature is kept in whole process, is warming up to after being added dropwise 60~80 DEG C, continue 24~30h of reaction, the reaction solution of gained is filtered, washing, dry fluorine sulfanilic.
  5. 5. a kind of method that imidodisulfuryl fluoride lithium salt is prepared using phthalimide according to claim 1, its It is characterised by, step C detailed process is that the 2- methylol benzoyl fluoride sulfimides shown in formula iii are dissolved in organic solution, After being cooled to -5~0 DEG C, alkali is added thereto, it is -5~0 DEG C that reaction temperature is kept in whole process, is warming up to after being added dropwise 60~80 DEG C, continue 24~30h of reaction, for the reaction solution of gained after decompression removes organic solvent, organic phase is collected in extraction, is received The organic phase of collection obtains fluorine sulfonamide after drying and removing water, vacuum distillation removing organic solvent.
  6. 6. a kind of method that imidodisulfuryl fluoride lithium salt is prepared using phthalimide according to claim 1, its It is characterised by, in step C, described acid is hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, boric acid, 4- benzyls sulfuric acid or methylsulfuric acid, institute The alkali stated is sodium hydroxide, potassium hydroxide, lithium hydroxide, potassium carbonate, sodium carbonate, potassium phosphate, sodium phosphate or sodium hydride, acid or alkali Dosage and formula iii shown in the mol ratios of 2- methylol benzoyl fluoride sulfimides be 2.5~3.5：1.
  7. 7. a kind of method that imidodisulfuryl fluoride lithium salt is prepared using phthalimide according to claim 1, its It is characterised by, the detailed process that the 2- methylol benzoyl fluoride sulfimides shown in iii carry out sulfuryl amine reaction with chlorine fluorine sulphonyl is 2- methylol benzoyl fluoride sulfimides shown in formula iii are dissolved in organic solution, alkaline reagent is added, is cooled to -20~-10 After DEG C, chlorine fluorine sulphonyl is slowly added dropwise thereto, it is -20~-10 DEG C that reaction temperature is kept during whole dropwise addition, after being added dropwise 20~35 DEG C are warming up to, continues 12~24h of reaction, after being evaporated under reduced pressure and removing solvent, extraction collection has the reaction solution of gained Machine phase, then obtain double fluorine sulfimides shown in formula v after being evaporated under reduced pressure and removing organic solvent；
    The detailed process that 2- methylol benzoyl fluoride sulfimides shown in iii carry out sulfuryl amine reaction with fluorosulfuric acid is by formula iii Shown 2- methylol benzoyl fluoride sulfimides are dissolved in organic solution, after being cooled to -20~-10 DEG C, are slowly added dropwise thereto Fluorosulfuric acid, it is -20~-10 DEG C that reaction temperature is kept during whole dropwise addition, and 20~35 DEG C are warming up to after being added dropwise, and is continued anti- 12~24h is answered, for the reaction solution of gained after being evaporated under reduced pressure and removing solvent, organic phase is collected in extraction, then is removed through being evaporated under reduced pressure Double fluorine sulfimides shown in formula v are obtained after organic solvent.
  8. 8. a kind of method that imidodisulfuryl fluoride lithium salt is prepared using phthalimide according to claim 1, its It is characterised by, step E detailed process forms double fluorine sulphurs for double fluorine sulfimides and resin lithium are dissolved in organic solvent respectively Imide solution and resin lithium solution, after resin lithium solution is cooled into 0~5 DEG C, double fluorine sulfimides are slowly added dropwise thereto Solution, the whole process holding reaction temperature that is added dropwise is 0 DEG C~5 DEG C, after being added dropwise, in the situation that keeping temperature is 0 DEG C~5 DEG C Under, continue 8~12h of reaction, filtered after having reacted, filtrate is recrystallized to give double fluorine sulphonyl after being evaporated under reduced pressure and removing solvent Imines lithium salts.
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