CN102786452A - Preparation method of bis(sulfonyl fluoride) imine and (perfluoroalkyl sulfonyl fluorine sulfonyl) imine alkali metal salt - Google Patents

Preparation method of bis(sulfonyl fluoride) imine and (perfluoroalkyl sulfonyl fluorine sulfonyl) imine alkali metal salt Download PDF

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CN102786452A
CN102786452A CN201210262032XA CN201210262032A CN102786452A CN 102786452 A CN102786452 A CN 102786452A CN 201210262032X A CN201210262032X A CN 201210262032XA CN 201210262032 A CN201210262032 A CN 201210262032A CN 102786452 A CN102786452 A CN 102786452A
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imine
fsi
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周志彬
韩洪波
聂进
刘凯
郭鹏
周宜轩
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Wuhan Ruihua New Energy Technology Co.,Ltd.
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Huazhong University of Science and Technology
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Abstract

The invention discloses a method for preparing bis(sulfonyl fluoride) imine and (perfluoroalkyl sulfonyl fluorine sulfonyl) imine alkali metal salt. According to the method, sulfamide is utilized to take reaction with thionyl chloride and chlorosulfonic acid for preparing bis(sulfonyl fluoride) imine or (perfluoroalkyl sulfonyl fluorine sulfonyl) imine, then, the bis(sulfonyl fluoride) imine or (perfluoroalkyl sulfonyl fluorine sulfonyl) imine takes reaction with antimony trifluoride and potassium (rubidium or caesium and the like) carbonate, and corresponding high-purity bis(sulfonyl fluoride) imine potassium (rubidium or caesium) salt or (perfluoroalkyl sulfonyl fluorine sulfonyl) imine potassium (rubidium or caesium) salt can be obtained; and the double decomposition exchange reaction of the potassium (rubidium or caesium) salt and lithium (or sodium) perchlorate or lithium (or sodium) tetrafluoroborate and the like in aprotic polar solvents is utilized to obtain corresponding high-purity lithium (or sodium) salt. The method provided by the invention has the characteristics that the operation step is simple, the products can be easily separated and purified, the purity and the yield are high, the environment pollution is avoided, the method is suitable for industrial mass production, and the like.

Description

The preparation method of two (fluorine sulphonyl) imines and (perfluoroalkyl group sulfonyl fluorosulfonyl) imines an alkali metal salt
Technical field
It is synthetic to the invention belongs to fluorine chemistry, relates to the preparation method of fluorine-containing imines an alkali metal salt, is specifically related to two (fluorine sulphonyl) imines (H [N (SO 2F) 2]) and (perfluoroalkyl group sulfonyl fluorosulfonyl) imines (H [R fSO 2NSO 2F], R f=C mF 2m+1, (M [N (the SO of an alkali metal salt m=1-8) 2F) 2], M [R fSO 2NSO 2F)]; M=Li, Na, K, Rb, preparation Cs).
Background technology
Two (fluorine sulphonyl) imines (H [N (SO 2F) 2], hereinafter to be referred as H [FSI]) and (perfluoroalkyl group sulfonyl fluorosulfonyl) imines (H [R fSO 2NSO 2F)], R f=C mF 2m+1, m=1-8; Hereinafter to be referred as H [R fFSI]) an alkali metal salt; Lithium salts particularly; It is important fluorine-containing organic ion compound; They, all have important commercial application and are worth with fields such as high-performance nonaqueous electrolyte material and efficient catalysts at clean energy devices such as serondary lithium battery, ultracapacitor and aluminium electrolutic capacitors.
The general structure of two (fluorine sulphonyl) imines and (perfluoroalkyl group sulfonyl fluorosulfonyl) imines an alkali metal salt is shown in the formula (I):
Figure BDA00001936067700011
Wherein: M +Be Li, Na, K, Rb or Cs,
R f＝C mF 2m+1，m＝0-8。
During m=0 two (fluorine sulphonyl) imines (H [N (SO 2F) 2] be called for short H [FSI]) and an alkali metal salt (M [FSI], M=Li, Na, K, Rb or Cs); During m=1-8 (perfluoroalkyl group sulfonyl fluorosulfonyl) imines (H [R fSO 2NSO 2F]), be called for short H [R fFSI]; R f=C mF 2m+1, (M [the Rf of an alkali metal salt m=1-8) FSI]; M=Li, Na, K, Rb or Cs).
An alkali metal salt (M [N (the SO of relevant H [FSI] in the prior art 2F) 2], M=Li, Na, K, Rb, preparation method Cs) can be divided into two types, and one type is step synthesis, and another kind of is one-step synthesis.
Step synthesis mainly adopts three step building-up reactionss: 1) synthetic two (chlorine sulphonyl) imines (H [N (SO 2Cl) 2]) (R.Appel et al, Chem.Ber.1962,95,625; R.Appel et al, 1962,95,1753; M.Becke-Goehring et al, Inorg.Synth.1966,8,105; J.K.Ruff, Inorg.Chem.1967,6,2108; E.A.Fadia, US 4315935,1982; M.Berran etal, Z.Anorg.Allg.Chem.2005,631,55) or chlorine sulphonyl trichlorine phosphonitrile (ClSO 2N=PCl 3) (J.K.Ruff, Inorg.Chem.1967,6,2108); 2) with HN (SO 2Cl) 2Or ClSO 2N=PCl 3Fluoridize (like AsF 3Or SbF 3As fluorizating agent) be converted into two (fluorine sulphonyl) imines (H [FSI]) (J.K.Ruff et al, Inorg.Synth.1968,11,138; B.Krumm et al, Inorg.Chem.1998,37,6295); 3) under low temperature-78 ℃, H [FSI] prepares corresponding alkali metal salt (J.K.Ruff et al, Inorg.Synth.1968,11,138 with alkaline carbonate through the acid-alkali neutralization reaction; J.K.Ruff, Inorg.Chem.1965,4,1446).This preparation method second, and three-step reaction, have following distinct disadvantage: 1) use AsF 3When preparing H [FSI], FSO is arranged in the reaction process as fluorizating agent 3H (165 ℃ of boiling points) generates, and the boiling point of its boiling point and product H [FSI] is very near (170 ℃ of boiling points) (J.K.Ruff et al, Inorg.Synth.1968,11,138); Product H [FSI] and by product POCl 3Form azeotrope (H [FSI] .POCl 3, 1: 1) and (J.K.Ruff, Inorg.Chem.1967,6,2108), and boiling point and FSO 3H is approaching, causes the separation of H [FSI] to purify very difficult.In addition, AsF 3Toxicity is big, and mass preparation causes severe contamination to environment.2) SbF 3During as fluorizating agent, its by product SbCl 3Be prone to distillation, during underpressure distillation, steam with product H [FSI].Thereby, through the method for underpressure distillation purify H [FSI] very the difficulty (B.Krumm et al, Inorg.Chem.1998,37,6295).The 3rd) an alkali metal salt of step prepared in reaction H [FSI] need be accomplished down at extremely low temperature (78 ℃); This mainly is because strong acid H [FSI] very exothermic when being dissolved in water; May cause S-F key hydrolysis in H [FSI] molecule, make H [FSI] decompose (J.K.Ruff, Inorg.Chem.1965; 4,1446; M.Lustig, Inorg.Chem.1964,3,01165; M.Berran et al, Z. Anorg.Allg.Chem.2005,631,55).Thereby, a large amount of preparation manipulation inconvenience.
In sum, there is all not high shortcoming of purification separation difficulty, product purity and productive rate in the method that the substep of existing bibliographical information prepares H [FSI] and an alkali metal salt thereof, is difficult to satisfy the high purity requirement of electrolyte.In addition, because harsh reaction conditions, a large amount of uses of severe corrosive or toxic chemical make existing compound method not satisfy the requirement of large-scale industrial production.
The one-step synthesis of an alkali metal salt of H [FSI] is with HN (SO 2Cl) 2React in organic solvent with excessive Potassium monofluoride (KF) etc., directly prepare the sylvite (hereinafter to be referred as K [FSI]) of H [FSI].This prepares route, not only has hypertoxic gas HF to generate, and excess reactant KF and product K [FSI] are owing to being insoluble in the organic solvent; Reaction system can condense into piece; The separation purification operations is relatively more difficult, loaded down with trivial details etc. (M.Cernik et al, US 7253317,2007; M.Beran et al, Polyhedron, 2006,25,1292; A.Hammami et al, US 2007043231,2007).
(perfluoroalkyl group sulfonyl fluorosulfonyl) imines (H [R fFSI]) be one type of asymmetric imines.Synthesizing of the asymmetric imines of relevant this type, bibliographical information is few.Up to the present, only relevant for (trifluoromethyl sulfonyl fluorosulfonyl) imines (H [CF 3FSI]) the synthetic report.Its compound method has: 1) by trifluoromethyl sulphonamide (CF 3SO 2NH 2) and phosphorus pentachloride (PCl 5) reaction makes trifluoromethyl sulphonyl trichlorine phosphonitrile (CF 3SO 2N=PCl 3) midbody, further with fluosulfonic acid (FSO 3H) reaction obtains H [CF 3FSI].This preparation method exists productive rate extremely low (less than 15%), by product POCl 3Remove trouble, raw material FSO 3Distinct disadvantage such as the very corrosive of H (H.W.Roesky et al, Inorg.Nucl.Chem.Letts, 1974,7,171; H.W.Roesky et al, Zeitschrift Fuer Naturforschung B, 1970,25,252).2) with trifluoromethyl sulphonamide (CF 3SO 2NH 2) and difluoro sulfone (FSO 2F) gas is raw material, at weak nucleophilic property alkaline matter triethylamine ((C 2H 5) 3N) under the catalysis, obtain H [CF 3FSI].Because FSO 2The use of F gas makes this method severe reaction conditions, complex operation, the productive rate of product also not high (D.H.Richard et al, US5874616,1999); 3) by trifluoromethyl sulphonyl trichlorine phosphonitrile (CF 3SO 2N=PCl 3) compound and chlorsulfonic acid (ClSO 3H) reaction or chlorine sulphonyl trichlorine phosphonitrile ((ClSO 2N=PCl 3)) and trifluoromethane sulfonic acid (CF 3SO 3H) reaction makes (trifluoromethyl sulfonyl chlorine sulphonyl) imines (HN (SO 2Cl) (SO 2CF 3)), this method is synthesized HN (SO 2Cl) (SO 2CF 3) productive rate higher, but with HN (SO 2Cl) (SO 2CF 3) when fluoridizing with fluorination reagent reaction, problem (K.Xu et al, Inorg.Chem.Commun.1999,2,26) such as same product separation difficulty, purity is not high in the time of can running into aforesaid preparation H [FSI].4) by trifluoromethyl sulphonamide sylvite (CF 3SO 2NHK) with fluorosulfonic anhydride (FSO 2) 2O) prepared in reaction, but fluorosulfonic anhydride is hypertoxic, thereby, be not suitable for a large amount of preparations (S.Maehama et al, JP 2005200359,2005).
Summary of the invention
The object of the present invention is to provide a kind of two (fluorine sulphonyl) imines (H [N (SO 2F) 2], be called for short H [FSI]) and (perfluoroalkyl group sulfonyl fluorosulfonyl) imines (H [R fSO 2NSO 2F]), be called for short H [R fFSI]; R f=C mF 2m+1, an alkali metal salt m=1-8) (M [FSI], M [R fFSI]; M=Li; Na; K, Rb, preparation method Cs); Make that it has that operation steps is simple, the easily separated purification of product, purity and productive rate height, non-environmental-pollution, be suitable for characteristics such as industrial mass production, existing method operation is cumbersome, productive rate is low to overcome, use the toxic agent contaminate environment, use unworkable fluoro-gas reagent, the product lock out operation is loaded down with trivial details, product is difficult for deficiencies such as purification.
Preparing method of the present invention utilizes substituted sulphonamide and thionyl chloride, chlorsulfonic acid to react, and makes two (chlorine sulphonyl) imines (H [N (SO 2Cl) 2]) or (perfluoroalkyl group sulfonyl chlorosulfonyl) imines (H [R fSO 2NSO 2Cl]) midbody; Two (chlorine sulphonyl) imines (H [N (SO 2Cl) 2]) or (perfluoroalkyl group sulfonyl chlorosulfonyl) imines (H [R fSO 2NSO 2Cl)) react with antimony trifluoride and salt of wormwood " original position one kettle ways " such as (cesium carbonate or rubidium carbonates) respectively, obtain two (fluorine sulphonyl) imines potassium (caesium or the rubidium) salt (M of corresponding high purity title product 1[FSI], M 1=K, Rb, Cs) or (perfluoroalkyl group sulfonyl fluorosulfonyl) imines potassium (caesium or rubidium) salt (M 1[R fFSI)], M 1=K, Rb, Cs), its structural formula is seen formula (II); Through this an alkali metal salt (M 1[FSI] or M 1[R fFSI)], M 1=K, Rb Cs) with the metathesis exchange reaction of (like methylcarbonate, acetonitrile, Nitromethane 99Min. etc.) in aprotic polar solvent such as lithium perchlorate (or sodium) or LiBF4 (or sodium), obtains highly purified corresponding lithium (or sodium) salt (M 2[FSI] or M 2[R fFSI)], M 2=Li, Na), its structural formula is seen formula (III).
Realize that concrete technical scheme of the present invention is:
1. the method for an alkali metal salt of preparation formula (II),
Figure BDA00001936067700051
Wherein: M 1 +Be K, Rb or Cs,
R f＝C mF 2m+1，m＝0-8，
Present method may further comprise the steps:
(1) be that mixing in 1: 2: 1～1: 3: 1 places reaction flask in molar ratio with sulphonamide, thionyl chloride, chlorsulfonic acid;
(2) reacted 20～24 hours down at 110～130 ℃, reducing pressure then steams group with imine moiety;
(3) under argon shield, with group with imine moiety and SbF 3The ratio that is 3: 2～4: 3 in molar ratio under agitation is mixed in the reaction flask;
(4) said mixture was at room temperature reacted 10～12 hours, add the solvent acetonitrile or the MTBE of 2～4 times of volumes then;
(5) under agitation, gradation is with 2～5 times, and preferred 2～3 Anhydrous potassium carbonates in the group with imine moiety mole number, cesium carbonate or rubidium carbonate solid join in the above-mentioned organic solution;
(6) add salt of wormwood, cesium carbonate or rubidium carbonate continued reaction 5～20 hours, be generally 10～12 hours, then, the pH value of reaction system is transferred to neutrality;
(7) filtration under diminished pressure, the filtering insolubles will be considered liquid and concentrated, and boil off 3/5～4/5 solvent;
(8) in above-mentioned steps (7) gained filtrating, add CH 2Cl 2Recrystallization after solid filtering, drying, obtains colourless sylvite, cesium salt or rubidium salt solid.
Sulphonamide described in the above-mentioned steps (1) can be substituted sulphonamide R f' SO 2NH 2, wherein: R f'=C mF 2mX, when m=0, X=OH; When m=1-8, X=F.
2. the method for preparing an alkali metal salt of formula III,
Figure BDA00001936067700061
Wherein, M 2 +Be Li or Na, R f=C mF 2m+1, m=0-8,
Present method is with an alkali metal salt of formula II and waits the perchloric acid of mole number or the lithium salts or the sodium salt of Tetrafluoroboric acid in organic aprotic polar solvent, to carry out metathesis exchange reaction, obtains corresponding colourless lithium salts or sodium salt.Described herein is the organic salt of solubilized formula II such as methylcarbonate, acetonitrile or Nitromethane 99Min. or III but do not dissolve KBF 4Or KClO 4Organic aprotic polar solvent of inorganic salt.
The another kind of method of an alkali metal salt of preparation formula provided by the invention (III) is: will wait in the filtrating of step (7) gained described in the method for perchloric acid or the lithium salts of Tetrafluoroboric acid or an alkali metal salt that sodium salt joins aforementioned preparation formula (II) of mole number; Stir 3～5 hours after-filtration under the room temperature, add CH 2Cl 2Recrystallization after solid filtering, drying, obtains colourless lithium salts or sodium salt solid.
Preparing method of the present invention is at synthetic asymmetric imines (perfluoroalkyl group sulfonyl fluorosulfonyl) imines (H [R fSO 2NSO 2F]) innovative point of an alkali metal salt is to have adopted the synthetic route different with existing document, avoids existing method productive rate low (like aforementioned employing CF 3SO 2N=PCl 3) or use toxic agent (like aforementioned employing (FSO 2) 2O) or use unworkable fluoro-gas reagent (like aforementioned employing FSO 2F).
The present invention is with chlorine sulfimide (H [N (SO at imines an alkali metal salt preparing method's innovative point 2Cl) 2] and H [R fSO 2NSO 2Cl]) compound uses SbF 3After carrying out fluoridation, promptly add Anhydrous potassium carbonate (caesium or rubidium) without isolation of intermediate products.This both can make H [FSI] or H [R through neutralization reaction fFSI] potassium (caesium or rubidium) salt, and the H that reaction produces 2O and excessive salt of wormwood (caesium or rubidium) can promote byproduct of reaction SbCl again 3Hydrolysis generates Sb 2O 3And KCl.Because Sb 2O 3Be insoluble to organic solvents such as acetonitrile with KCl, can with filtering method they be separated with title product easily, overcome in the step synthesis of existing bibliographical information because of SbCl 3Distillation causes fatal shortcomings such as the product lock out operation is loaded down with trivial details, the difficult purification of product, has also avoided product caking in the one-step synthesis, operates cumbersome shortcoming.
Adopt synthetic H [FSI] of the inventive method and H [R fFSI] an alkali metal salt, productive rate and purity easy and simple to handle, product are all very high, can as the lithium salts in the ionogen or be used for Preparation of catalysts and high-performance ion liquid synthetic.
Description of drawings
Accompanying drawing 1: two (fluorosulfonyl) imines sylvite (K [FSI]) 19F NMR spectrum.
Accompanying drawing 2: the infrared spectrogram of two (fluorosulfonyl) imines sylvite (K [FSI]); V (cm -1): 1387 (v As, SO 2), 1222,1184 (v s, SO 2).
Accompanying drawing 3: (trifluoromethyl sulfonyl fluorosulfonyl) imines sylvite (K [CF 3FSI]) 19F NMR spectrum.
Accompanying drawing 4: (trifluoromethyl sulfonyl fluorosulfonyl) imines sylvite (K [CF 3FSI]) infrared spectrogram; V (cm -1): 1358 (v As, SO 2), 1208,1186 (v s, SO 2).
Embodiment
Enumerate part of compounds involved in the present invention preparation below, the present invention being done further detailed explanation, but the preparation method of embodiment is not restricted to the preparation of cited compound.
Embodiment 1-11 relates to H [FSI] and H [R fFSI] preparation method of an alkali metal salt.
Embodiment 1: the preparation of two (fluorine sulphonyl) imines potassium (K [FSI])
The building-up reactions route is following:
HOSO 2NH 2+SOCl 2+HOSO 2Cl→H[N(SO 2Cl) 2]+SO 2↑+HCl↑
Figure BDA00001936067700082
Under the nitrogen protection; Thionamic acid, the thionyl chloride of 1780 grams (15mol), 580 gram (0.5mol) chlorsulfonic acids of 480 grams (5mol) are joined in the 5000mL reaction flask successively; 130 ℃ of stirring reactions 24 hours, excessive lower boiling reactant was removed in air distillation, carries out underpressure distillation then; Collect the cut of 112-114 ℃/2mmHg, obtain two (chlorine sulphonyl) imines (HN (SO under the room temperature 2Cl) 2) colourless crystallization 880 grams (4.1mol), productive rate 82%.
Under magnetic agitation and nitrogen protection, with two (chlorine sulphonyl) imines of 96 grams (0.45mol), and the anhydrous antimony trifluoride of 54 grams (0.3mol) places the there-necked flask of 500mL, stirs reaction down under the room temperature after 12 hours, in reaction flask, adds the acetonitrile of 350mL.After treating the dissolving of most of solid, under agitation divide 15 times 166 gram (1.2mol) Anhydrous potassium carbonate solids slowly to be added in the reaction flask, add continued reaction 12 hours.Then, extremely neutral with the pH value of 2M HCl regulation system.
Filtration under diminished pressure is removed solid insoluble, and filtrating is concentrated into about 70mL, adds isopyknic CH 2Cl 2Carry out recrystallization.Filtration, washing, drying, the colourless crystallization solid 77 that gets two (fluorine sulphonyl) imines potassium (K [FSI]) restrains (0.35mol), productive rate 78%. 19F NMR (acetone-d 6, CCl 3F, 376.5MHz): δ=51.4ppm (s) (seeing accompanying drawing 1).Ir spectra is seen accompanying drawing 2.
Embodiment 2: the preparation of two (fluorine sulphonyl) imines caesium (Cs [FSI])
The building-up reactions route is following:
Figure BDA00001936067700091
Under magnetic agitation and nitrogen protection; Two (chlorine sulphonyl) imines (pressing embodiment 1 operation preparation) with 9.6 grams (0.045mol); And the anhydrous antimony trifluoride of 5.4 grams (0.03mol) places the there-necked flask of 100mL; Stir reaction down under the room temperature after 12 hours, in reaction flask, add the acetonitrile of 40mL.After treating most of solid dissolving, gradation under agitation adds 8.9 gram (0.03mol) Carbon Dioxide caesiums to reaction flask, adds continued reaction 12 hours.Then, extremely neutral with the pH value of 2M HCl regulation system.Filtration under diminished pressure is removed solid insoluble, and filtrating is concentrated into about 10mL, adds isopyknic CH 2Cl 2Carry out recrystallization.Filtration, washing, drying, the colourless crystallization solid 10.5 that gets two (fluorine sulphonyl) imines potassium (Cs [FSI]) restrains (0.034mol), productive rate 75%. 19F?NMR(acetone-d 6，CCl 3F，376.5MHz)：δ＝51.6ppm(s)。
Embodiment 3: the preparation of two (fluorine sulphonyl) imines lithium (Li [FSI])
The building-up reactions route is following:
Figure BDA00001936067700092
In vacuum glove box, the anhydrous acetonitrile of 91.5 gram (0.34mol) two (fluorine sulphonyl) imines potassium (K [FSI]), 250mL is joined in the there-necked flask of 500mL successively, after the stirring and dissolving, slowly splash into lithium perchlorate (LiClO under the room temperature 4) acetonitrile solution 150mL (contain 36.2 the gram LiClO 4), stirring reaction is 24 hours under the room temperature, static spending the night, and filtration under diminished pressure is removed insolubles potassium perchlorate (KClO 4), filtrating is concentrated into about 60mL, add isopyknic CH 2Cl 2Carry out recrystallization.Filtration, CH 2Cl 2Washing, vacuum-drying get 62 gram (0.33mol) white solid powder Li [FSI]. 19F?NMR(acetone-d 6，CCl 3F，376.5MHz)：δ＝51.8ppm(s)。
Embodiment 4: the preparation of two (fluorine sulphonyl) imines sodium (Na [FSI])
The building-up reactions route is following:
Figure BDA00001936067700101
In vacuum glove box, the K [FSI] of 87.7 grams (0.4mol), the acetonitrile of 250mL are joined in the there-necked flask of 500mL successively, after the dissolving of stirring at room solid, the sodium perchlorate (NaClO of 49.0 grams (0.4mol) 4) slowly join in the flask stirring reaction after 12 hours under the room temperature, hold over night, the undissolved potassium perchlorate of decompression elimination.Filtrating is concentrated into about 60mL, adds isopyknic CH 2Cl 2Carry out recrystallization.Filtration, washing, drying, 79.2 the gram (0.39mol) Na [FSI]. 19F?NMR(acetone-d 6，CCl 3F，376.5MHz)：δ＝51.6ppm(s)。
Embodiment 5: (trifluoromethyl sulfonyl fluorosulfonyl) imines potassium (K [CF 3FSI]) preparation
The building-up reactions route is following:
CF 3SO 2NH 2+SOCl 2+HOSO 2Cl→H[CF 3SO 2NSO 2Cl]+SO 2↑+HCl↑
Figure BDA00001936067700103
Under nitrogen protection, with the trifluoromethyl sulphonamide (CF of 7.5 grams (0.05mol) 3SO 2NH 2), 11.9 the gram (0.1mol) thionyl chloride, 6 the gram (0.05mol) chlorsulfonic acid join in the reaction flask successively; Stir following 120 ℃ of reactions 20 hours; Carry out underpressure distillation then, collect cut (the trifluoromethyl sulfonyl chlorine sulphonyl) imines (H [CF of 102-104 ℃/2mmHg 3SO 2NSO 2Cl]) colourless crystallization 9.3 grams, productive rate 75%.
Under magnetic agitation and argon shield, (the trifluoromethyl sulfonyl chlorine sulphonyl) imines of 7.4 grams (0.03mol) and the anhydrous antimony trifluoride of 7.2 grams (0.04mol) are placed the 100mL there-necked flask.Reaction added the MTBE (MBE) of 50mL after 10 hours under the room temperature in reaction flask.After treating most of solid dissolving, gradation under agitation slowly is added to the Anhydrous potassium carbonate of 0.1mol in the reaction flask, adds continued reaction 10 hours.Then, extremely neutral with the pH value of HCl regulation system.
Decompression elimination insolubles is concentrated into filtrating about 10mL, adds isopyknic CH 2Cl 2Carry out recrystallization.Filtration, washing, drying get 7 gram (0.026mol) K [CF 3FSI] the colourless crystallization solid, productive rate 87%. 19F NMR (acetone-d 6, CCl 3F, 376.5MHz): (s, 1F), (s 3F) (sees accompanying drawing 3) to-79.2ppm in δ=55.8.Ir spectra is seen accompanying drawing 4.
Embodiment 6: (trifluoromethyl sulfonyl fluorosulfonyl) imines lithium caesium (Cs [CF 3FSI]) preparation
The building-up reactions route is following:
Figure BDA00001936067700111
Under magnetic agitation and argon shield, (trifluoromethyl sulfonyl chlorine sulphonyl) imines (by embodiment 5 operation preparation) and 14.4 of 14.8 grams (0.06mol) is restrained (0.08mol) anhydrous antimony trifluorides place the 100mL there-necked flask.Reaction added the MTBE (MBE) of 100mL after 10 hours under the room temperature in reaction flask.After treating most of solid dissolving, gradation under agitation slowly is added to the Anhydrous potassium carbonate of 27 grams (0.2mol) in the reaction flask, adds continued reaction 10 hours.Then, extremely neutral with the pH value of 2MHCl regulation system.Decompression elimination insolubles is concentrated into filtrating about 18mL, adds isopyknic CH 2Cl 2Carry out recrystallization.Filtration, washing, drying get 20.6 gram Cs [CF 3FSI] the colourless crystallization solid, productive rate 95%. 19F?NMR(acetone-d 6，CCl 3F，376.5MHz)：δ＝56.1(s，1F)，-79.0ppm(s，3F)。
Embodiment 7: (trifluoromethyl sulfonyl fluorosulfonyl) imines lithium salts (Li [CF 3FSI]) preparation
The building-up reactions route is following:
Figure BDA00001936067700121
In vacuum glove box, with (0.25mol) (trifluoromethyl sulfonyl fluorosulfonyl) imines potassium (K [CF 3FSI]), the methylcarbonate of 200mL joins in the there-necked flask of 500mL successively, after the stirring and dissolving, slowly splashes into the LiBF4 (LiBF that is dissolved with (0.25mol) 4) methylcarbonate solution, stirring reaction is 12 hours under the room temperature, filtration under diminished pressure is removed undissolved potassium tetrafluoroborate.Filtrating is concentrated into 50mL continues to pressurize to take out to desolvate, get the Li [CF of 78 grams (0.24mol) 3FSI] .DMC title complex (1: 1), productive rate 96%. 1H?NMR(acetone-d 6，TMS，400MHz)：δ＝3.73ppm(s，OCH 3)。 19F?NMR(acetone-d 6，CCl 3F，376.5MHz)：δ＝56.2(s，1F)，-79.3ppm(s，3F)。
Embodiment 8: (trifluoromethyl sulfonyl fluorosulfonyl) imines sodium (Na [CF 3FSI]) preparation
The building-up reactions route is following:
With 81 gram (0.3mol) (trifluoromethyl sulfonyl fluorosulfonyl) imines potassium (K [CF 3FSI]), the 250mL acetonitrile joins in the there-necked flask of 500mL successively, under agitation after the dissolving, the sodium perchlorate of 0.3mol slowly joined in the flask stirring at room reaction 10 hours, decompression elimination insolubles potassium perchlorate.Filtrating is concentrated into about 60mL, adds isopyknic CH 2Cl 2Carry out recrystallization.Filtration, washing, drying get 73 gram (0.29mol) Na [CF 3FSI] solid. 19F?NMR(acetone-d 6，CCl 3F，376.5MHz)：δ＝56.1(s，1F)，-79.1ppm(s，3F)。
Embodiment 9: (pentafluoroethyl group fluorosulfonyl alkylsulfonyl) imines potassium (K [C 2F 5FSI]) preparation
The building-up reactions route is following:
C 2F 5SO 2NH 2+SOCL 2+HOSO 2CL←H[C 2F 5SO 2NSO 2CL]+SO 2↑+HCL↑
Figure BDA00001936067700132
Under the nitrogen protection, with 20 gram (0.1mol) pentafluoroethyl group sulphonamide (C 2F 5SO 2NH 2), 36 gram (0.3mol) thionyl chlorides, 12 gram (0.1mol) chlorsulfonic acids join reaction flask successively and cause, and stir down 120 ℃ of reactions 24 hours, carry out underpressure distillation then, 21 gram (perfluor ethylsulfonyl chlorine sulphonyl) imines (H [C 2F 5SO 2NSO 2Cl]), productive rate 70%.
Under magnetic agitation and nitrogen protection, 8.9 gram (0.03mol) (perfluor ethylsulfonyl chlorine sulphonyl) imines and 7.2 gram (0.04mol) anhydrous antimony trifluorides are placed the 100mL there-necked flask.Reaction added the MTBE (MBE) of 50mL after 10 hours under the room temperature in reaction flask.After treating most of solid dissolving, gradation under agitation slowly is added to 14 gram (0.1mol) Anhydrous potassium carbonates in the reaction flask, adds continued reaction 11 hours.Then, extremely neutral with the pH value of 2M HCl regulation system.
Filtration under diminished pressure is removed insolubles, and filtrating is concentrated into about 12mL, adds isopyknic CH 2Cl 2Carry out recrystallization.Filtration, washing, drying get 8.9 gram (0.028mol) K [C 2F 5FSI] solid, productive rate 93%. 19F?NMR(acetone-d 6，CCl 3F，376.5MHz)：δ＝56.2(s，1F)，-79.8(s，3F)，-118.0(2F)ppm(s)。
Embodiment 10: (perfluor normal-butyl fluorosulfonyl alkylsulfonyl) imines potassium (K [n-C 4F 9FSI]) preparation
The building-up reactions route is following:
n-C 4F 9SO 2NH 2+SOCl 2+HOSO 2Cl→H[n-C 4F 9SO 2NSO 2Cl]+SO 2↑+HCl↑
Figure BDA00001936067700134
With 30 gram (0.1mol) perfluoro butyl sulphonamide (n-C 4F 9SO 2NH 2), 36 gram (0.3mol) thionyl chlorides, 36 gram (0.1mol) chlorsulfonic acids join in the reaction flask successively, stir down 130 ℃ of reactions 22 hours, carry out underpressure distillation then, 28 gram (perfluoro butyl alkylsulfonyl chlorine sulphonyl) imines (H [n-C 4F 9SO 2NSO 2Cl]) colourless crystallization, productive rate 70%.
Under magnetic agitation and argon shield, with 14 gram (0.05mol) (perfluoro butyl alkylsulfonyl chlorine sulphonyl) imines (H [n-C 4F 9SO 2NSO 2Cl]) and the anhydrous antimony trifluoride of 27 grams (0.15mol) place the there-necked flask of 250mL.Reaction added the acetonitrile of 100mL after 12 hours under the room temperature in reaction flask.After treating most of solid dissolving, gradation under agitation slowly is added to the Anhydrous potassium carbonate of 14 grams (0.1mol) in the reaction flask, adds continued reaction 12 hours.Then, extremely neutral with the pH value of HCl regulation system.
Filtration under diminished pressure is removed insolubles, and filtrating is concentrated into about 20mL, adds isopyknic CH 2Cl 2Carry out recrystallization.Filtration, washing, drying get 19 gram (0.045mol) K [C 4F 9FSI] the colourless crystallization solid, productive rate 90%. 19F?NMR(acetone-d 6，CCl 3F，376.5MHz)：δ＝56.3(s，1F)，-81.8(3F)，-113.6(s，2F)，-121.8(s，2F)，-126.6ppm(s，2F)。
Embodiment 11: (perfluor n-octyl fluorosulfonyl alkylsulfonyl) imines potassium (K [n-C 8F 17FSI]) preparation
The building-up reactions route is following:
n-C 8F 17SO 2NH 2+SOCl 2+HOSO 2Cl→H[n-C 8F 17SO 2NSO 2Cl]+SO 2↑+HCl↑
With 100 gram (0.2mol) perfluor n-octyl sulphonamide (n-C 8F 17SO 2NH 2), 72 the gram (0.6mol) thionyl chlorides, 24 the gram (0.2mol) chlorsulfonic acids join successively in the reaction flask, stir following 130 ℃ the reaction 24 hours, carry out underpressure distillation then, (perfluor type octyl group sulphur alkylsulfonyl chlorine sulphonyl) imines (H [n-C 8F 17SO 2NSO 2Cl]) solid 78 grams, productive rate 65%.
Under magnetic agitation and argon shield, with 60 gram (0.1mol) (perfluor type octyl group alkylsulfonyl chlorine sulphonyl) imines (H [n-C 8F 17SO 2NSO 2Cl]) and 18 the gram (0.1mol) anhydrous antimony trifluoride place the 500mL there-necked flask.Reaction added the acetonitrile of 200mL after 12 hours under the room temperature in reaction flask.After treating most of solid dissolving, gradation under agitation slowly is added to 39 gram (0.3mol) Anhydrous potassium carbonates in the reaction flask, adds continued reaction 12 hours.Then, extremely neutral with the pH value of HCl regulation system.
Decompression elimination insolubles, volatile matter is removed in underpressure distillation, adds 80mLCH 2Cl 2Recrystallization.Filtration, washing, drying get 56 gram (0.090mol) K [n-C 8F 17FSI] solid, productive rate 90%. 19F?NMR(acetone-d 6，CCl 3F，376.5MHz)：δ＝56.3(s，1F)，-81.6(s，3F)，-113.4(s，2F)，-120.8(s，2F)，-122.2-122.4(m，3×2F)，-123.3(s，2F)，-126.6ppm(s，2F)。

Claims (2)

1. method for preparing an alkali metal salt of formula (III),
Figure FDA00001936067600011
Wherein, M 2 +Be Li or Na, R f=C mF 2m+1, m=0-8,
It is characterized in that, may further comprise the steps:
(1) be that mixing in 1: 2: 1～1: 3: 1 places reaction flask in molar ratio with sulphonamide, thionyl chloride, chlorsulfonic acid;
(2) reacted 20～24 hours down at 110～130 ℃, reducing pressure then steams group with imine moiety;
(3) under argon shield, with group with imine moiety and SbF 3The ratio that is 3: 2～4: 3 in molar ratio under agitation is mixed in the reaction flask;
(4) said mixture was at room temperature reacted 10～12 hours, add the solvent acetonitrile or the MTBE of 2～4 times of volumes then;
(5) under agitation, gradation is with 2～5 times, and preferred 2～3 Anhydrous potassium carbonates in the group with imine moiety mole number, cesium carbonate or rubidium carbonate solid join in the above-mentioned organic solution;
(6) add salt of wormwood, cesium carbonate or rubidium carbonate continued reaction 5～20 hours, be generally 10～12 hours, then, the pH value of reaction system is transferred to neutrality;
(7) filtration under diminished pressure, the filtering insolubles, will filtrate concentrates, and boils off 3/5～4/5 solvent;
(8) will wait the perchloric acid of mole number or the lithium salts or the sodium salt of Tetrafluoroboric acid to join in step (7) the gained filtrating, stir 3～5 hours after-filtration under the room temperature, add isopyknic CH 2Cl 2Recrystallization after solid filtering, drying, obtains colourless lithium salts or sodium salt solid.
2. the method for an alkali metal salt of preparation formula according to claim 1 (III) is characterized in that, described sulphonamide is substituted sulphonamide R f' SO 2NH 2, wherein: R f'=C mF 2mX, when m=0, X=OH; When m=1-8, X=F.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104151206A (en) * 2013-05-14 2014-11-19 华中科技大学 Alkali metal salt of (sulfonyl fluoride)( multi-fluorine alkoxy sulfonyl) imine and ionic liquids
CN104671224A (en) * 2013-11-27 2015-06-03 张家港市国泰华荣化工新材料有限公司 Synthesis method for bis(fluorosulfonyl)imide salt
CN106167455A (en) * 2013-07-11 2016-11-30 隆萨有限公司 For the method preparing imide two sulfonyl compound
CN114408882A (en) * 2021-12-30 2022-04-29 石家庄康坦福化工科技有限公司 Preparation and application of lithium bis (fluorosulfonyl) imide

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5723664A (en) * 1994-09-12 1998-03-03 Central Glass Company, Limited Method of preparing sulfonimide or its salt
JP2005200359A (en) * 2004-01-16 2005-07-28 Tosoh Corp Ionic compound
US20070043231A1 (en) * 2005-08-22 2007-02-22 Amer Hammami Process for preparing sulfonylimides and derivatives thereof
US7253317B2 (en) * 2000-12-29 2007-08-07 Hydro-Quebec Method for fluorinating a compound comprising a halosulphonyl or dihalophosphonyl group

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5723664A (en) * 1994-09-12 1998-03-03 Central Glass Company, Limited Method of preparing sulfonimide or its salt
US7253317B2 (en) * 2000-12-29 2007-08-07 Hydro-Quebec Method for fluorinating a compound comprising a halosulphonyl or dihalophosphonyl group
JP2005200359A (en) * 2004-01-16 2005-07-28 Tosoh Corp Ionic compound
US20070043231A1 (en) * 2005-08-22 2007-02-22 Amer Hammami Process for preparing sulfonylimides and derivatives thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
BURKHARD KRUMM等: ""Synthesis of Poly- and the First Perfluoroalkyl-N(SO2F)2 Derivatives: Improved Methods", 《INORG. CHEM.》 *
MARTIN BERAN等: ""A new route to the syntheses of alkali metal bis(fluorosulfuryl)imides: Crystal structure of LiN(SO2F)2"", 《POLYHEDRON》 *
MARTIN BERAN等: ""Eine neue Methode zur Darstellung von Imido-bis(schwefelsäure)dihalogeniden, (F,Cl), und das Kaliumsalz von Imido-bis(schwefelsäure)difluorid"", 《Z. ANORG. ALLG. CHEM.》 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104151206A (en) * 2013-05-14 2014-11-19 华中科技大学 Alkali metal salt of (sulfonyl fluoride)( multi-fluorine alkoxy sulfonyl) imine and ionic liquids
CN106167455A (en) * 2013-07-11 2016-11-30 隆萨有限公司 For the method preparing imide two sulfonyl compound
CN106167455B (en) * 2013-07-11 2018-09-14 隆萨有限公司 The method for being used to prepare two sulfonyl compound of imide
CN104671224A (en) * 2013-11-27 2015-06-03 张家港市国泰华荣化工新材料有限公司 Synthesis method for bis(fluorosulfonyl)imide salt
CN104671224B (en) * 2013-11-27 2016-10-12 江苏国泰超威新材料有限公司 The synthetic method of double fluorine sulfimide salt
CN114408882A (en) * 2021-12-30 2022-04-29 石家庄康坦福化工科技有限公司 Preparation and application of lithium bis (fluorosulfonyl) imide

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