CN102786452B - 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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CN102786452B
CN102786452B CN201210262032.XA CN201210262032A CN102786452B CN 102786452 B CN102786452 B CN 102786452B CN 201210262032 A CN201210262032 A CN 201210262032A CN 102786452 B CN102786452 B CN 102786452B
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imine
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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) imine alkali metal salt
Technical field
The invention belongs to fluorine chemistry synthetic, relate to the preparation method of fluorine-containing imine alkali metal salt, be 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, Cs) preparation.
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 ionic compounds, 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) imine alkali metal salt is shown in formula (I):
Figure BDA00001936067700011
Wherein: M +li, Na, K, Rb or Cs,
R f＝C mF 2m+1，m＝0-8。
During m=0, be two (fluorine sulphonyl) imines (H[N (SO 2f) 2] be called for short H[FSI]) an alkali metal salt (M[FSI], M=Li, Na, K, Rb or Cs); During m=1-8, be (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[Rf m=1-8) fsI]; M=Li, Na, K, Rb or Cs).
Relevant H[FSI in prior art] an alkali metal salt (M[N (SO 2f) 2], M=Li, Na, K, Rb, Cs) preparation method can be divided into two classes, a class is step synthesis, 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) by HN (SO 2cl) 2or ClSO 2n=PCl 3fluoridize (as 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) at low temperature-78 ℃, H[FSI] by acid-alkali neutralization reaction, prepare corresponding an alkali metal salt (J.K.Ruff et al, Inorg.Synth.1968,11,138 with alkaline carbonate; J.K.Ruff, Inorg.Chem.1965,4,1446)., there is following distinct disadvantage in this preparation method's second and three-step reaction: 1) uses AsF 3as fluorizating agent, prepare H[FSI] time, FSO in reaction process, had 3h (165 ℃ of boiling points) generates, its boiling point and product H[FSI] boiling point very approach (170 ℃ of boiling points) (J.K.Ruff et al, Inorg.Synth.1968,11,138); Product H[FSI] and by product POCl 3formation azeotrope (H[FSI] .POCl 3, 1: 1) and (J.K.Ruff, Inorg.Chem.1967,6,2108), and boiling point and FSO 3h approaches, and causes H[FSI] separating-purifying very difficult.In addition, AsF 3toxicity is large, and extensive preparation causes severe contamination to environment.2) SbF 3during as fluorizating agent, its by product SbCl 3easily distillation, during underpressure distillation, with product H[FSI] together with steam.Thereby, by the method for the underpressure distillation H[FSI that purifies] very difficult (B.Krumm et al, Inorg.Chem.1998,37,6295).The 3rd) step reaction preparation H[FSI] an alkali metal salt need under extremely low temperature (78 ℃), complete, this is mainly due to strong acid H[FSI] very exothermic while being dissolved in water, may cause H[FSI] S-F key hydrolysis in 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, the substep of existing bibliographical information is prepared H[FSI] and the method for an alkali metal salt there is all shortcomings such as not high of purification separation difficulty, product purity and productive rate, be difficult to meet the high purity requirement of electrolyte.In addition, due to harsh reaction conditions, a large amount of uses of severe corrosive or toxic chemical, make existing synthetic method not meet the requirement of large-scale industrial production.
H[FSI] the one-step synthesis of an alkali metal salt, be by HN (SO 2cl) 2react in organic solvent with excessive Potassium monofluoride (KF) etc., directly prepare H[FSI] sylvite (hereinafter to be referred as K[FSI]).This syntheti c route, not only has hypertoxic gas HF to generate, and excess reactant KF and product K[FSI] owing to being all insoluble in organic solvent, reaction system can condense into piece, separating-purifying operation is 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 the asymmetric imines of a class.Synthesizing of the asymmetric imines of relevant this class, bibliographical information is few.Up to the present, only relevant for (trifluoromethyl sulfonyl fluorosulfonyl) imines (H[CF 3fSI]) synthetic report.Its synthetic method has: 1) by trimethyl fluoride sulfonyl amine (CF 3sO 2nH 2) and phosphorus pentachloride (PCl 5) reaction makes trimethyl fluoride sulfonyl trichlorine phosphonitrile (CF 3sO 2n=PCl 3) intermediate, further with fluosulfonic acid (FSO 3h) reaction obtains H[CF 3fSI].There is productive rate extremely low (being less than 15%), by product POCl in this preparation method 3remove trouble, raw material FSO 3distinct disadvantage (H.W.Roesky et al, Inorg.Nucl.Chem.Letts, 1974,7,171 such as the corrodibility of H is extremely strong; H.W.Roesky et al, Zeitschrift Fuer Naturforschung B, 1970,25,252).2) with trimethyl fluoride sulfonyl amine (CF 3sO 2nH 2) and difluoro sulfone (FSO 2f) gas is raw material, at weak nucleophilic alkaline matter triethylamine ((C 2h 5) 3n) under catalysis, obtain H[CF 3fSI].Due to FSO 2the use of F gas, makes the method severe reaction conditions, complex operation, and the productive rate of product is not high (D.H.Richard et al, US5874616,1999) also; 3) by trimethyl fluoride sulfonyl 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)), the method is synthesized HN (SO 2cl) (SO 2cF 3) productive rate higher, but by HN (SO 2cl) (SO 2cF 3) react with fluorination reagent while fluoridizing, can run into and aforesaid preparation H[FSI] time the problems (K.Xu et al, Inorg.Chem.Commun.1999,2,26) such as same product separation difficulty, purity is not high.4) by trimethyl fluoride sulfonyl amine sylvite (CF 3sO 2nHK) with fluorosulfonic anhydride (FSO 2) 2o) reaction preparation, 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, Cs) preparation method, make it have that operation steps is simple, the easily separated purification of product, purity and productive rate is high, non-environmental-pollution, be suitable for the features such as industrial mass production, to overcome, existing method operation is cumbersome, productive rate is low, use toxic agent contaminate environment, use unworkable fluoro-gas reagent, product separation complex operation, product are difficult for the deficiencies such as purification.
Preparation method of the present invention utilizes the sulphonamide of replacement to react with thionyl chloride, chlorsulfonic acid, makes two (chlorine sulphonyl) imines (H[N (SO 2cl) 2]) or (perfluoroalkyl group sulfonyl chlorosulfonyl) imines (H[R fsO 2nSO 2cl]) intermediate; 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 (cesium carbonate or rubidium carbonate) etc. " original position one kettle way " respectively, obtain two (fluorine sulphonyl) imines potassium (caesium or the rubidium) salt (M of corresponding high purity target 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 shown in formula (II); By this alkali metal salt (M 1[FSI] or M 1[R ffSI)], M 1=K, Rb, Cs) with the metathesis exchange reaction of (as methylcarbonate, acetonitrile, Nitromethane 99Min. etc.) in aprotic polar solvent such as lithium perchlorate (or sodium) or LiBF4 (or sodium), obtain highly purified corresponding lithium (or sodium) salt (M 2[FSI] or M 2[R ffSI)], M 2=Li, Na), its structural formula is shown in formula (III).
Realizing 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 +k, Rb or Cs,
R f＝C mF 2m+1，m＝0-8，
Present method comprises the following steps:
(1) by sulphonamide, thionyl chloride, chlorsulfonic acid, be within 1: 2: 1～1: 3: 1, to mix to be placed in reaction flask in molar ratio;
(2) at 110～130 ℃, react 20～24 hours, then reduce pressure group with imine moiety is steamed;
(3) under argon shield, by group with imine moiety and SbF 3the ratio that is in molar ratio 3: 2～4: 3 is under agitation mixed in reaction flask;
(4) said mixture is at room temperature reacted 10～12 hours, then add solvent acetonitrile or the methyl tertiary butyl ether of 2～4 times of volumes;
(5) under agitation, gradation is by 2～5 times, and preferably 2～3 Anhydrous potassium carbonates in group with imine moiety mole number, cesium carbonate or rubidium carbonate solid, join in above-mentioned organic solution;
(6) add after salt of wormwood, cesium carbonate or rubidium carbonate and continue reaction 5～20 hours, be generally 10～12 hours, then, the pH value of reaction system is adjusted to neutrality;
(7) filtration under diminished pressure, filtering insolubles, will consider liquid and concentrate, and boil off 3/5～4/5 solvent;
(8) in above-mentioned steps (7) gained filtrate, add CH 2cl 2recrystallization, by solid filtering, dry after, obtain colourless sylvite, cesium salt or rubidium salt solid.
Sulphonamide described in above-mentioned steps (1) can be the sulphonamide R of replacement 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,
Wherein, M 2 +li or Na, R f=C mf 2m+1, m=0-8,
Present method is by an alkali metal salt of formula II and waits the perchloric acid of mole number or the lithium salts of Tetrafluoroboric acid or sodium salt 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 the 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 the perchloric acid of mole number or the lithium salts of Tetrafluoroboric acid or sodium salt to join in the filtrate of step (7) gained described in the method for an alkali metal salt of aforementioned preparation formula (II), under room temperature, stir after 3～5 hours and filter, add CH 2cl 2recrystallization, by solid filtering, dry after, obtain colourless lithium salts or sodium salt solid.
Preparation 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 from existing document, avoids existing method productive rate low (as aforementioned employing CF 3sO 2n=PCl 3) or use toxic agent (as aforementioned employing (FSO 2) 2o) or use unworkable fluoro-gas reagent (as aforementioned employing FSO 2f).
The present invention is by chlorine sulfimide (H[N (SO at imine alkali metal salt preparation method's innovative point 2cl) 2] and H[R fsO 2nSO 2cl]) compound SbF 3carry out after fluoridation, without isolation of intermediate products, add Anhydrous potassium carbonate (caesium or rubidium).This both can make H[FSI by neutralization reaction] or H[R 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.Due to Sb 2o 3be insoluble to the organic solvents such as acetonitrile with KCl, can be easily by the method for filtering, they are separated with target product, overcome in the step synthesis of existing bibliographical information because of SbCl 3distillation causes product separation complex operation, product to be difficult for the fatal shortcomings such as purification, has also avoided product caking in one-step synthesis, operates cumbersome shortcoming.
Adopt the 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 be as the lithium salts in ionogen or for the preparation of catalyzer and synthesizing of high-performance ionic liquid.
Accompanying drawing explanation
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 preparation involved in the present invention below, so that the present invention is 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])
Building-up reactions route is as follows:
HOSO 2NH 2+SOCl 2+HOSO 2Cl→H[N(SO 2Cl) 2]+SO 2↑+HCl↑
Figure BDA00001936067700082
Under nitrogen protection; the thionyl chloride of the thionamic acid of 480 grams (5mol), 1780 grams (15mol), 580 grams of (0.5mol) chlorsulfonic acids are joined in 5000mL reaction flask successively; 130 ℃ of stirring reactions 24 hours; excessive lower boiling reactant is removed in air distillation; then carry out underpressure distillation; collect the cut of 112-114 ℃/2mmHg, under room temperature, obtain two (chlorine sulphonyl) imines (HN (SO 2cl) 2) 880 grams of colourless crystallizations (4.1mol), productive rate 82%.
Under magnetic agitation and nitrogen protection; by two (chlorine sulphonyl) imines of 96 grams (0.45mol); and the anhydrous antimony trifluoride of 54 grams (0.3mol) is placed in the there-necked flask of 500mL, under room temperature, stir lower reaction after 12 hours, to the acetonitrile that adds 350mL in reaction flask.After most of dissolution of solid, under agitation divide and 15 times 166 grams of (1.2mol) Anhydrous potassium carbonate solids are slowly added in reaction flask, add rear continuation reaction 12 hours.Then, extremely neutral by the pH value of 2M HCl regulation system.
Filtration under diminished pressure is removed solid insoluble, and filtrate is concentrated into 70mL left and right, adds isopyknic CH 2cl 2carry out recrystallization.Filter, washing, dry, obtain 77 grams of the colourless crystallization solids (0.35mol) of two (fluorine sulphonyl) imines potassium (K[FSI]), productive rate 78%. 19f NMR (acetone-d 6, CCl 3f, 376.5MHz): δ=51.4ppm (s) (seeing accompanying drawing 1).Infrared spectra is shown in accompanying drawing 2.
Embodiment 2: the preparation of two (fluorine sulphonyl) imines caesium (Cs[FSI])
Building-up reactions route is as follows:
Figure BDA00001936067700091
Under magnetic agitation and nitrogen protection; by two (chlorine sulphonyl) imines of 9.6 grams (0.045mol) (pressing embodiment 1 operation preparation); and the anhydrous antimony trifluoride of 5.4 grams (0.03mol) is placed in the there-necked flask of 100mL; under room temperature, stir lower reaction after 12 hours, to the acetonitrile that adds 40mL in reaction flask.After most of dissolution of solid, under agitation gradation adds 8.9 grams of (0.03mol) Carbon Dioxide caesiums to reaction flask, adds rear continuation reaction 12 hours.Then, extremely neutral by the pH value of 2M HCl regulation system.Filtration under diminished pressure is removed solid insoluble, and filtrate is concentrated into 10mL left and right, adds isopyknic CH 2cl 2carry out recrystallization.Filter, washing, dry, obtain 10.5 grams of the colourless crystallization solids (0.034mol) of two (fluorine sulphonyl) imines potassium (Cs[FSI]), productive rate 75%. 19F?NMR(acetone-d 6，CCl 3F，376.5MHz)：δ＝51.6ppm(s)。
Embodiment 3: the preparation of two (fluorine sulphonyl) imine lithium (Li[FSI])
Building-up reactions route is as follows:
In vacuum glove box, the anhydrous acetonitrile of 91.5 grams (0.34mol) two (fluorine sulphonyl) imines potassium (K[FSI]), 250mL is joined in the there-necked flask of 500mL successively, after stirring and dissolving, under room temperature, slowly splash into lithium perchlorate (LiClO 4) acetonitrile solution 150mL (contain 36.2 grams of LiClO 4), under room temperature, stirring reaction is 24 hours, static spending the night, and filtration under diminished pressure, removes insolubles potassium perchlorate (KClO 4), filtrate is concentrated into 60mL left and right, add isopyknic CH 2cl 2carry out recrystallization.Filtration, CH 2cl 2washing, vacuum-drying, obtain 62 grams of (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])
Building-up reactions route is as follows:
Figure BDA00001936067700101
In vacuum glove box, by the K[FSI of 87.7 grams (0.4mol)], the acetonitrile of 250mL joins in the there-necked flask of 500mL successively, after stirring at room dissolution of solid, by the sodium perchlorate (NaClO of 49.0 grams (0.4mol) 4) slowly join in flask stirring reaction after 12 hours under room temperature, standing over night, the undissolved potassium perchlorate of decompression elimination.Filtrate is concentrated into 60mL left and right, adds isopyknic CH 2cl 2carry out recrystallization.Filter, wash, be dried, obtain the Na[FSI of 79.2 grams (0.39mol)]. 19F?NMR(acetone-d 6，CCl 3F，376.5MHz)：δ＝51.6ppm(s)。
Embodiment 5:(trifluoromethyl sulfonyl fluorosulfonyl) imines potassium (K[CF 3fSI]) preparation
Building-up reactions route is as follows:
CF 3SO 2NH 2+SOCl 2+HOSO 2Cl→H[CF 3SO 2NSO 2Cl]+SO 2↑+HCl↑
Under nitrogen protection, by the trimethyl fluoride sulfonyl amine (CF of 7.5 grams (0.05mol) 3sO 2nH 2), the thionyl chloride of 11.9 grams (0.1mol) is, the chlorsulfonic acid of 6 grams (0.05mol) joins in reaction flask successively; stir lower 120 ℃ of reactions 20 hours; then carry out underpressure distillation, collect cut (the trifluoromethyl sulfonyl chlorine sulphonyl) imines (H[CF of 102-104 ℃/2mmHg 3sO 2nSO 2cl]) 9.3 grams of colourless crystallizations, 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 in to 100mL there-necked flask.Under room temperature, react after 10 hours, to the methyl tertiary butyl ether (MBE) that adds 50mL in reaction flask.After most of dissolution of solid, under agitation gradation, by the Anhydrous potassium carbonate of 0.1mol, is slowly added in reaction flask, adds rear continuation reaction 10 hours.Then, extremely neutral by the pH value of HCl regulation system.
Decompression elimination insolubles, is concentrated into 10mL left and right by filtrate, adds isopyknic CH 2cl 2carry out recrystallization.Filter, wash, be dried, obtain 7 grams of (0.026mol) K[CF 3fSI] colourless crystallization solid, productive rate 87%. 19f NMR (acetone-d 6, CCl 3f, 376.5MHz): δ=55.8 (s, 1F) ,-79.2ppm (s, 3F) (seeing accompanying drawing 3).Infrared spectra is shown in accompanying drawing 4.
Embodiment 6:(trifluoromethyl sulfonyl fluorosulfonyl) imine lithium caesium (Cs[CF 3fSI]) preparation
Building-up reactions route is as follows:
Figure BDA00001936067700111
Under magnetic agitation and argon shield, (the trifluoromethyl sulfonyl chlorine sulphonyl) imines of 14.8 grams (0.06mol) (by embodiment 5 operation preparations) and 14.4 grams of (0.08mol) anhydrous antimony trifluorides are placed in to 100mL there-necked flask.Under room temperature, react after 10 hours, to the methyl tertiary butyl ether (MBE) that adds 100mL in reaction flask.After most of dissolution of solid, under agitation gradation, by the Anhydrous potassium carbonate of 27 grams (0.2mol), is slowly added in reaction flask, adds rear continuation reaction 10 hours.Then, extremely neutral by the pH value of 2MHCl regulation system.Decompression elimination insolubles, is concentrated into 18mL left and right by filtrate, adds isopyknic CH 2cl 2carry out recrystallization.Filter, wash, be dried, obtain 20.6 grams of Cs[CF 3fSI] 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
Building-up reactions route is as follows:
Figure BDA00001936067700121
In vacuum glove box, by (0.25mol) (trifluoromethyl sulfonyl fluorosulfonyl) imines potassium (K[CF 3fSI]), the methylcarbonate of 200mL joins in the there-necked flask of 500mL successively, after stirring and dissolving, slowly splashes into the LiBF4 (LiBF that is dissolved with (0.25mol) 4) methylcarbonate solution, under room temperature, stirring reaction is 12 hours, filtration under diminished pressure is removed undissolved potassium tetrafluoroborate.Filtrate is concentrated into 50mL continuation pressurization and pumps solvent, obtain 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
Building-up reactions route is as follows:
Figure BDA00001936067700122
By 81 grams (0.3mol) (trifluoromethyl sulfonyl fluorosulfonyl) imines potassium (K[CF 3fSI]), 250mL acetonitrile joins in the there-necked flask of 500mL successively, after under agitation dissolving, the sodium perchlorate of 0.3mol slowly joined in flask to stirring at room reaction 10 hours, decompression elimination insolubles potassium perchlorate.Filtrate is concentrated into 60mL left and right, adds isopyknic CH 2cl 2carry out recrystallization.Filter, wash, be dried, obtain 73 grams of (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
Building-up reactions route is as follows:
C 2F 5SO 2NH 2+SOCL 2+HOSO 2CL←H[C 2F 5SO 2NSO 2CL]+SO 2↑+HCL↑
Figure BDA00001936067700132
Under nitrogen protection, by 20 grams of (0.1mol) pentafluoroethyl group sulphonamide (C 2f 5sO 2nH 2), 36 grams of (0.3mol) thionyl chlorides, 12 grams of (0.1mol) chlorsulfonic acids join successively reaction flask and cause, and under stirring, 120 ℃ of reactions 24 hours, then carry out underpressure distillation, obtain 21 grams of (perfluor ethylsulfonyl chlorine sulphonyl) imines (H[C 2f 5sO 2nSO 2cl]), productive rate 70%.
Under magnetic agitation and nitrogen protection, 8.9 grams (0.03mol) (perfluor ethylsulfonyl chlorine sulphonyl) imines and 7.2 grams of (0.04mol) anhydrous antimony trifluorides are placed in to 100mL there-necked flask.Under room temperature, react after 10 hours, to the methyl tertiary butyl ether (MBE) that adds 50mL in reaction flask.After most of dissolution of solid, under agitation gradation, by 14 grams of (0.1mol) Anhydrous potassium carbonates, is slowly added in reaction flask, adds rear continuation reaction 11 hours.Then, extremely neutral by the pH value of 2M HCl regulation system.
Filtration under diminished pressure is removed insolubles, and filtrate is concentrated into 12mL left and right, adds isopyknic CH 2cl 2carry out recrystallization.Filter, wash, be dried, obtain 8.9 grams of (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
Building-up reactions route is as follows:
n-C 4F 9SO 2NH 2+SOCl 2+HOSO 2Cl→H[n-C 4F 9SO 2NSO 2Cl]+SO 2↑+HCl↑
Figure BDA00001936067700134
By 30 grams of (0.1mol) perfluoro butyl sulphonamide (n-C 4f 9sO 2nH 2), 36 grams of (0.3mol) thionyl chlorides, 36 grams of (0.1mol) chlorsulfonic acids join in reaction flask successively; under stirring, at 130 ℃, react 22 hours; then carry out underpressure distillation, obtain 28 grams of (perfluoro butyl alkylsulfonyl chlorine sulphonyl) imines (H[n-C 4f 9sO 2nSO 2cl]) colourless crystallization, productive rate 70%.
Under magnetic agitation and argon shield, by 14 grams (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) be placed in the there-necked flask of 250mL.Under room temperature, react after 12 hours, to the acetonitrile that adds 100mL in reaction flask.After most of dissolution of solid, under agitation gradation, by the Anhydrous potassium carbonate of 14 grams (0.1mol), is slowly added in reaction flask, adds rear continuation reaction 12 hours.Then, extremely neutral by the pH value of HCl regulation system.
Filtration under diminished pressure is removed insolubles, and filtrate is concentrated into 20mL left and right, adds isopyknic CH 2cl 2carry out recrystallization.Filter, wash, be dried, obtain 19 grams of (0.045mol) K[C 4f 9fSI] 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
Building-up reactions route is as follows:
n-C 8F 17SO 2NH 2+SOCl 2+HOSO 2Cl→H[n-C 8F 17SO 2NSO 2Cl]+SO 2↑+HCl↑
Figure BDA00001936067700142
By 100 grams of (0.2mol) perfluor n-octyl sulphonamide (n-C 8f 17sO 2nH 2), 72 grams of (0.6mol) thionyl chlorides, 24 grams of (0.2mol) chlorsulfonic acids join in reaction flask successively, stir lower 130 ℃ of reactions 24 hours, then carry out underpressure distillation, (perfluor type octyl group sulphur alkylsulfonyl chlorine sulphonyl) imines (H[n-C 8f 17sO 2nSO 2cl]) 78 grams of solids, productive rate 65%.
Under magnetic agitation and argon shield, by 60 grams (0.1mol) (perfluor type octyl group alkylsulfonyl chlorine sulphonyl) imines (H[n-C 8f 17sO 2nSO 2cl]) and the anhydrous antimony trifluoride of 18 grams (0.1mol) be placed in 500mL there-necked flask.Under room temperature, react after 12 hours, to the acetonitrile that adds 200mL in reaction flask.After most of dissolution of solid, under agitation gradation, by 39 grams of (0.3mol) Anhydrous potassium carbonates, is slowly added in reaction flask, adds rear continuation reaction 12 hours.Then, extremely neutral by the pH value of HCl regulation system.
Decompression elimination insolubles, volatile matter is removed in underpressure distillation, adds 80mLCH 2cl 2recrystallization.Filter, wash, be dried, obtain 56 grams of (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. a method for an alkali metal salt of preparation formula (III),
Wherein, M 2 +li or Na, R f=C mf 2m+1, m=0-8,
It is characterized in that, comprise the following steps:
(1) sulphonamide, thionyl chloride, chlorsulfonic acid for mixing, 1:2:1～1:3:1 are placed in to reaction flask in molar ratio;
(2) at 110～130 ℃, react 20～24 hours, then reduce pressure group with imine moiety is steamed;
(3) under argon shield, by group with imine moiety and SbF3 in molar ratio for the ratio of 3:2～4:3 is under agitation mixed in reaction flask;
(4) said mixture is at room temperature reacted 10～12 hours, then add solvent acetonitrile or the methyl tertiary butyl ether of 2～4 times of volumes;
(5) under agitation, gradation, by 2～5 times of Anhydrous potassium carbonates to group with imine moiety mole number, cesium carbonate or rubidium carbonate solid, joins in above-mentioned organic solution;
(6) add after salt of wormwood, cesium carbonate or rubidium carbonate and continue reaction 5～20 hours, then, the pH value of reaction system is adjusted to neutrality;
(7) filtration under diminished pressure, filtering insolubles, filtrate is concentrated, boil off 3/5～4/5 solvent;
(8) by waiting the perchloric acid of mole number or the lithium salts of Tetrafluoroboric acid or sodium salt to join in step (7) gained filtrate, under room temperature, stir after 3～5 hours and filter, add isopyknic CH 2cl 2recrystallization, by solid filtering, dry after, obtain 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, the sulphonamide R of described sulphonamide for replacing 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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