JP5208782B2 - Fluorosulfonylimides and process for producing the same - Google Patents

Description

  The present invention relates to fluorosulfonylimides, and more particularly to derivatives such as N- (fluorosulfonyl) -N- (fluoroalkylsulfonyl) imide, di (fluorosulfonyl) imide and salts thereof, and a method for producing the same.

Fluorosulfonylimides such as N- (fluorosulfonyl) -N- (fluoroalkylsulfonyl) imide, di (fluorosulfonyl) imide and the like, and their salts are N (SO ₂ F) groups or N (SO ₂ F) Useful as an intermediate for a compound having _two groups, an additive for an electrolyte, a fuel cell electrolyte, a selective electrophilic fluorinating agent, a photoacid generator, a thermal acid generator, It is a useful compound in various applications, such as being used as a near infrared absorbing dye.

For example, the above di (fluorosulfonyl) imide has been conventionally prepared by subjecting di (chlorosulfonyl) imide to a halogen exchange reaction using a fluorinating agent. For example, in Non-Patent Document 1, arsenic trifluoride (AsF ₃ ) is used as the fluorinating agent in Non-Patent Document 2, and antimony trifluoride (SbF ₃ ) is used as the fluorinating agent. A method for fluorinating di (chlorosulfonyl) imide using an ionic fluoride of a monovalent cation such as CsF as a fluorinating agent is described. Patent Document 2 discloses a method for preparing di (fluorosulfonyl) imide by distilling fluorosulfonic acid (HFSO ₃ ) in the presence of urea.

JP-T-2004-522681 JP-T 8-511274

John K. Ruff and Max Lustig, Inorg. Synth. 11,138-140 (1968) Jean’ne M. Shreeve et al., Inorg. Chem. 1998, 37 (24), 6295-6303

However, when AsF ₃ is used as the fluorinating agent, it is difficult to avoid the generation of by-products that are difficult to separate from the product, and AsF ₃ is relatively expensive. In addition, although the problem of a by-product is eliminated by using SbF ₃ instead of AsF ₃ , since these As and Sb are both highly toxic elements, it is desired to refrain from using them as much as possible. . In the method described in Patent Document 2, hydrogen fluoride is generated during the reaction. Since hydrogen fluoride is a highly toxic and corrosive substance, if it is contained in the product, it can be used as a peripheral component when using di (fluorosulfonyl) imide as a salt in various applications. May corrode. Accordingly, there is a need for a method for producing di (fluorosulfonyl) imides in which such substances are not by-produced.

  Furthermore, the production method described in Patent Document 1 has a problem that a long time is required for the reaction.

  The present invention has been made paying attention to these circumstances, and its purpose is to suppress the formation of by-products, and to make N- (fluorosulfonyl) -N— more safely, quickly and efficiently. It is in providing the manufacturing method from which fluorosulfonyl imides, such as (fluoroalkyl sulfonyl) imide and di (fluoro sulfonyl) imide, these salts, etc. are obtained, and fluoro sulfonyl imides.

  The production method of the present invention that has solved the above problems is a production method of a fluorosulfonylimide salt represented by the following scheme, in which a compound represented by the general formula (I) in the following scheme is reacted with an onium salt. A step of obtaining an onium salt of chlorosulfonylimide represented by the general formula (II), an onium salt of the chlorosulfonylimide, an element of Group 11 to Group 15 and Group 4 to Period 6 (provided that arsenic) And a step of obtaining a compound represented by the general formula (III) by reacting with a fluoride containing at least one element selected from the group consisting of (excluding antimony and antimony). doing.

In formula (I) or formula (II) in the above scheme, R ³ is fluorine, chlorine or a fluorinated alkyl group having 1 to 6 carbon atoms, R ^{4 in} formula (III) is fluorine or a fluorinated alkyl group, R ⁵ in the formulas (II) and (III) is an onium cation, and n corresponds to the valence of the onium cation R ⁵ and represents an integer of 1 to 3.

The fluoride preferably contains at least one element selected from the group consisting of Cu, Zn and Bi, and the compound represented by the general formula (I) is a starting material such as cyan chloride (CNCl) or amide. It is desirable that it is obtained using sulfuric acid (HSO ₃ NH ₂ ).

  It is preferable to further include a step of further reacting the compound represented by the general formula (III) obtained by the above-described method with an alkali metal salt to obtain a compound represented by the following general formula (VII).

In the formula (VII), R ² represents an alkali metal, R ⁴ represents fluorine or a fluorinated alkyl group having 1 to 6 carbon atoms, and 1 is 1.

  Fluorosulfonylimide salt obtained by the above-described production method and represented by the formula (III) in the above scheme, and fluorosulfonylimide salt (VII) which is a reaction product of the general formula (III) and an alkali metal salt Are also included in the present invention.

  In this specification, the expression “fluorosulfonylimide” means N ((fluorosulfonyl) imide having two fluorosulfonyl groups, N- (fluorosulfonyl) imide, fluorosulfonyl group, and fluoroalkylsulfonyl group, unless otherwise specified. Sulfonyl) -N- (fluoroalkylsulfonyl) imide. The same applies to “chlorosulfonylimide”. The “fluoroalkyl” means a fluorinated alkyl group in which one or more hydrogen atoms are substituted with a fluorine atom in an alkyl group having 1 to 6 carbon atoms, and examples thereof include a fluoromethyl group, a difluoromethyl group, and trifluoro A methyl group, a fluoroethyl group, a difluoroethyl group, a trifluoroethyl group, a pentafluoroethyl group and the like are included.

  According to the present invention, since the fluorination reaction is performed after chlorosulfonylimide is converted to an onium salt, heat generation is suppressed, and the fluorination reaction can proceed more safely. In addition, by appropriately selecting the reaction solvent, the metal salt produced by the fluorination reaction can be easily removed and the solvent can be efficiently removed, so that the workability of the purification process is improved. Furthermore, according to the present invention, the production of by-products can be suppressed without using expensive fluorinating agents such as antimony (Sb) and arsenic (As), which is more efficient than conventional methods. Often, N- (fluorosulfonyl) -N- (fluoroalkylsulfonyl) imide and di (fluorosulfonyl) imide and salts thereof are obtained.

  The production method of the present invention is a production method of a fluorosulfonylimide salt such as di (fluorosulfonyl) imide salt and N- (fluorosulfonyl) -N- (fluoroalkylsulfonyl) imide salt represented by the following scheme, A step of reacting a compound represented by the general formula (I) and an onium salt in the following scheme to obtain an onium salt of the chlorosulfonylimide represented by the general formula (II), an onium salt of the chlorosulfonylimide, By reacting with a fluoride containing at least one element selected from the group consisting of elements of Groups 11 to 15 and Groups 4 to 6 (excluding arsenic and antimony), the compound represented by the general formula (III And the step of obtaining a compound represented by

In the scheme 1, R ³ is fluorine (F), chlorine (Cl), or a fluorinated alkyl group having 1 to 6 carbon atoms, R ⁴ is fluorine or a fluorinated alkyl group, R ⁵ is an onium cation, n corresponds to the valence of the onium cation R ⁵ and represents an integer of 1 to 3.

  Hereinafter, the production method of the present invention will be described in detail. First, in the manufacturing method of this invention, the compound represented by general formula (I) and the onium salt are made to react in the said scheme 1, and the compound represented by general formula (II) (onium of chlorosulfonyl imide) Salt).

Examples of the compound represented by the general formula (I) include compounds in which R ³ is fluorine, chlorine, or a fluorinated alkyl group having 1 to 6 carbon atoms. The fluorinated alkyl group preferably has 1 to 4 carbon atoms, more preferably 1 to 2. Specific fluorinated alkyl groups include fluoromethyl group, difluoromethyl group, trifluoromethyl group, fluoroethyl group, difluoroethyl group, 2,2,2-trifluoroethyl group, pentafluoroethyl group, 3,3 , 3-trifluoropropyl group, perfluoro-n-propyl group, fluoropropyl group, perfluoroisopropyl group, fluorobutyl group, 3,3,4,4,4-pentafluorobutyl group, perfluoro-n-butyl group, perfluoro Isobutyl group, perfluoro-t-butyl group, perfluoro-sec-butyl group, fluoropentyl group, perfluoropentyl group, perfluoroisopentyl group, perfluoro-t-pentyl group, fluorohexyl group, perfluoro-n-hexyl group, perfluoroiso Hexyl group It is. Among these, a trifluoromethyl group, a pentafluoroethyl group, and a perfluoro-n-propyl group are preferable, and a trifluoromethyl group and a pentafluoroethyl group are more preferable.

  A commercially available compound may be used as the compound represented by the general formula (I), but it can also be synthesized using cyanogen chloride (CNCl) as a starting material (Scheme 2).

R ³ in formula (I) is as described above.

For example, in the case of synthesizing di (chlorosulfonyl) imide in which R ³ is chlorine in formula (I), anhydrous sulfuric acid (SO ₃ ) and chlorosulfonic acid may be reacted with cyanogen chloride. At this time, first, cyanogen chloride and sulfuric anhydride are reacted (scheme 2, compound (IV) → compound (V)). The mixing ratio of these starting materials is preferably 1: 0.5 to 1:10 (cyanogen chloride: sulfuric anhydride, molar ratio). More preferably, it is 1: 1 to 1: 5.

  Conditions for reacting cyanogen chloride with sulfuric anhydride are not particularly limited and can be appropriately adjusted according to the progress of the reaction. For example, the reaction temperature is preferably 0 ° C. to 100 ° C. (more preferably 10 ° C. to 50 ° C.), and the reaction time may be 0.1 hour to 48 hours (more preferably 1 hour to 24 hours). . The reaction is preferably carried out without solvent, but a solvent may be used if necessary. As the solvent, an aprotic solvent described later is preferably used.

Subsequently, the obtained chlorosulfonyl isocyanate (ClSO ₂ NCO, the above formula (V)) is reacted with chlorosulfonic acid to obtain di (chlorosulfonyl) imide (the above formula (I), R ³ is Cl). . The mixing ratio of chlorosulfonyl isocyanate (compound (V)) and chlorosulfonic acid is preferably 1: 0.5 to 1: 2 (chlorosulfonyl isocyanate: chlorosulfonic acid, molar ratio), more preferably 1 : 0.8 to 1: 1.2.

  The reaction of chlorosulfonyl isocyanate and chlorosulfonic acid is carried out at 50 ° C. to 200 ° C. (more preferably 70 ° C. to 180 ° C.) under an inert gas atmosphere for 0.1 hour to 48 hours (more preferably 1 hour). Up to 24 hours). Chlorosulfonic acid is liquid and functions as a solvent during the synthesis reaction, but other solvents may be used as necessary.

N- (chlorosulfonyl) -N- (fluoroalkylsulfonyl) imide in which R ³ is a fluorinated alkyl group having 1 to 6 carbon atoms in the above general formula (I) is chlorosulfonyl isocyanate and fluorinated alkylsulfonic acid. Or a reaction of fluorinated alkylsulfonyl isocyanate and chlorosulfonic acid. A preferred compound is trifluoromethanesulfonic acid.

  The compounding ratio of chlorosulfonyl isocyanate (compound (V)) and fluorinated alkyl compound is preferably 1: 0.5 to 1: 2 (chlorosulfonyl isocyanate: fluoroalkyl compound, molar ratio), more preferably 1: 0.8 to 1: 1.2. The reaction conditions can be the same as when di (chlorosulfonyl) imide is synthesized.

N- (chlorosulfonyl) -N- (fluorosulfonyl) imide in which R ³ is fluorine in the above formula (I) is a reaction between chlorosulfonyl isocyanate and fluorosulfonic acid, or fluorosulfonyl isocyanate and chlorosulfonic acid. Is obtained by reaction with The same amount of starting material as in the case of di (chlorosulfonyl) imide can be adopted as the compounding amount and reaction conditions.

  Furthermore, the above di (chlorosulfonyl) imide can also be synthesized by reacting amide sulfuric acid and thionyl chloride and then further reacting with chlorosulfonic acid (for example, Z. Anorg. Allg. Chem 2005, 631). , 55-59).

  The mixing ratio of amidosulfuric acid and thionyl chloride is preferably 1: 1 to 1:20 (amidosulfuric acid: thionyl chloride, molar ratio), more preferably 1: 2 to 1:10. The mixing ratio of chlorosulfonic acid is preferably 1: 0.5 (amidosulfuric acid: chlorosulfonic acid, molar ratio) with respect to amidosulfuric acid, more preferably 1: 1 to 1: 5.

  The conditions for reacting thionyl chloride and chlorosulfonic acid with amidosulfuric acid are not particularly limited, and may be appropriately adjusted according to the progress of the reaction. For example, the reaction temperature is preferably 0 ° C. to 200 ° C., more preferably 50 ° C. to 150 ° C., and the reaction may be performed while raising the temperature stepwise within this temperature range. The reaction time is preferably 0.1 hour to 100 hours, more preferably 1 to 50 hours. The reaction is preferably carried out without a solvent, but a solvent may be used if necessary.

  Next, the obtained compound (I) is reacted with an onium salt to obtain a compound represented by the general formula (II) (an onium salt of chlorosulfonylimide). Prior to the fluorination of Cl, the chlorosulfonylimides are made into an onium salt, so that heat generation during the fluorination reaction can be suppressed as compared with the case of having a proton, that is, in the imide form.

  As the onium salt, a salt composed of an onium cation and an anion represented by the following general formula (VI) is preferably used. Preferred anions include halogen ions such as fluorine, chlorine, bromine and iodine, hydroxide ions, carbonate ions and bicarbonate ions.

(In the formula, L represents C, Si, N, P, S or O. R is the same or different and each represents hydrogen or an organic group, and two or more thereof may be bonded to each other.) Is 2, 3 or 4, and is a value determined by the valence of the element L. The bond between L and R may be a single bond or a double bond.)
Specific examples of the onium cation represented by the general formula (VI) include those having a structure represented by the following general formula. In the formula, R is the same as in the general formula (VI).

  These onium cations may be used alone or in combination of two or more. Among the onium cations having the above structure, the following onium cations (1) to (4) are preferable.

  (1) One of nine heterocyclic onium cations represented by the following general formula.

(2) One of five types of unsaturated onium cations represented by the following general formula.

(3) One of 10 types of saturated ring onium cations represented by the following general formula.

In the above general formula, R ^{6 to} R ¹⁷ are the same or different and are hydrogen or an organic group, and two or more of these may be bonded to each other.

(4) A chain onium cation in which R is hydrogen or an alkyl group having 1 to 8 carbon atoms. Among these, those in which L is N in the general formula (VII) are preferable. For example, tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, tetraheptylammonium, tetrahexylammonium, tetraoctylammonium, triethylmethylammonium, methoxyethyldiethylmethylammonium, trimethylphenylammonium, benzyltrimethylammonium, benzyltributylammonium , Benzyltriethylammonium, dimethyldistearylammonium, diallyldimethylammonium, quaternary ammoniums such as 2-methoxyethoxymethyltrimethylammonium, tetrakis (pentafluoroethyl) ammonium, trimethylammonium, triethylammonium, diethylmethylammonium, dimethyl Tertiary ammoniums such as ethylammonium, dibutylmethylammonium and tributylammonium, secondary ammoniums such as dimethylammonium, diethylammonium and dibutylammonium, methylammonium, ethylammonium, butylammonium, hexylammonium and octylammonium Examples include primary ammoniums, N-methoxytrimethylammonium, N-ethoxytrimethylammonium, N-propoxytrimethylammonium, and ammonium compounds such as NH ₄ . Among these, ammonium, trimethylammonium, triethylammonium, tributylammonium, triethylmethylammonium, tetraethylammonium and diethylmethyl (2-methoxyethyl) ammonium are mentioned as preferable chain onium cations.

  Among the onium cations of the above (1) to (4), preferred are the following general formulas:

(Wherein R ^{6 to} R ¹⁷ are the same as above), and the chain onium cation of (4) above. The organic group of R ^{6 to} R ¹⁷ is preferably a linear, branched, or cyclic saturated or unsaturated hydrocarbon group having 1 to 18 carbon atoms, a fluorine group, or the like, more preferably 1 to 8 carbon atoms. A saturated or unsaturated hydrocarbon group or a fluorocarbon group. These organic groups are hydrogen atom, fluorine atom, amino group, imino group, amide group, ether group, ester group, hydroxyl group, carboxyl group, carbamoyl group, cyano group, sulfone group, sulfide group, nitrogen atom, oxygen An atom, a sulfur atom, etc. may be included. More preferably, it has any one or more of a hydrogen atom, a fluorine atom, a cyano group and a sulfone group. In addition, when two or more organic groups are bonded, the bond may be formed between the main skeleton of the organic group, or between the main skeleton of the organic group and the above-described substituent, or It may be formed between the above substituents.

  In the reaction from compound (I) to (II) in Scheme 1 above, the compounding ratio of the compound represented by formula (I) and the onium salt is 1: 0.5 to 1:10 (molar ratio). Is preferable. More preferably, it is 1: 1 to 1: 5. In the exchange reaction from proton to onium cation, the chlorosulfonylimide represented by the general formula (I) and the onium salt may be mixed in the presence of a solvent. The temperature at this time is 0 ° C. to 200 ° C. (more preferably 1 ° C. to 100 ° C.), and the reaction may be performed for 0.1 hour to 48 hours (more preferably 0.1 hour to 24 hours). Examples of the solvent include ethylene carbonate, propylene carbonate, butylene carbonate, γ-butyrolactone, γ-valerolactone, dimethoxymethane, 1,2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxane, 4-methyl. -1,3-dioxolane, methyl formate, methyl acetate, methyl propionate, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, sulfolane, 3-methyl sulfolane, dimethyl sulfoxide, N, N-dimethylformamide, N-methyloxazolidinone An aprotic solvent such as valeronitrile, benzonitrile, ethyl acetate, isopropyl acetate, butyl acetate, nitromethane, nitrobenzene and the like can be used. From the viewpoint of workability at the time of purification, a solvent having a low boiling point and capable of forming a two-layer state with water is preferable. Among the solvents exemplified above, valeronitrile, ethyl acetate, isopropyl acetate and butyl acetate are preferable.

  Subsequently, the obtained onium salt of chlorosulfonylimide represented by the general formula (II) and the elements of Groups 11 to 15 and 4 to 6 (excluding arsenic and antimony) By reacting with a fluoride containing at least one element selected from the group, a compound represented by the general formula (III) is obtained (Scheme 1, Compound (II) → Compound (III)).

The fluoride containing at least one element selected from the group consisting of the elements of Groups 11 to 15 and Periods 4 to 6 (excluding arsenic and antimony) includes 2 of the above elements. What contains the element used as the cation more than valence is preferable. Specifically, preferred fluorides include elements that become divalent cations such as Cu, Zn, Sn, and Pb, and elements that become trivalent cations such as Bi. More preferred fluorides include CuF ₂ , ZnF ₂ , SnF ₂ , PbF ₂ and BiF ₃ , still more preferably CuF ₂ , ZnF ₂ and BiF ₃ , and even more preferably ZnF ₂ .

  The compounding ratio of the onium salt of chlorosulfonylimide represented by the general formula (II) and the above-mentioned fluoride is when di (chlorosulfonyl) imide (compound (II)) is reacted with a divalent fluoride. In this case, the ratio is preferably 1: 0.8 to 1:10 (compound (II): fluoride, molar ratio), more preferably 1: 1 to 1: 5, and still more preferably 1: 1 to 1. 1: 2. In the case of reacting with a trivalent fluoride, the ratio is preferably 1: 0.5 to 1: 7, more preferably 1: 0.7 to 1: 3, and still more preferably 1: 0.7-1: 1.3. On the other hand, when N- (chlorosulfonyl) -N- (fluoroalkylsulfonyl) imide or N- (fluorosulfonyl) -N- (chlorosulfonyl) imide is used as the compound (II), it is reacted with a divalent fluoride. The blending ratio at that time is preferably 1: 0.4 to 1: 5 (compound (II): fluoride, molar ratio). More preferably, it is 1: 0.5 to 1: 2.5, further preferably 1: 0.5 to 1: 1, and in the case of reacting with a trivalent fluoride, 1: 0.3 ˜1: 3 is preferable, more preferably 1: 0.3 to 1: 0.8, and still more preferably 1: 0.3 to 1: 0.7. If the blending amount of the fluoride is too small, there is a possibility that an unreacted chlor body may remain. On the other hand, if the blending amount of the fluoride is too large, it is difficult to remove the unreacted raw material.

  The reaction conditions for obtaining compound (III) from compound (II) may be appropriately adjusted according to the progress of the reaction, but preferably the reaction temperature is 0 ° C to 200 ° C (more preferably 10 ° C to 100 ° C.) and a reaction time of 0.1 to 48 hours (more preferably 1 to 24 hours) is recommended.

  The reaction solvent is not necessarily used when the starting materials are liquid and are dissolved in each other. For example, ethylene carbonate, propylene carbonate, butylene carbonate, γ-butyrolactone, γ-valerolactone, dimethoxymethane, 1 , 2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxane, 4-methyl-1,3-dioxolane, methyl formate, methyl acetate, methyl propionate, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate , Acetonitrile, sulfolane, 3-methylsulfolane, dimethyl sulfoxide, N, N-dimethylformamide, N-methyloxazolidinone, valeronitrile, benzonitrile, ethyl acetate, isopropyl acetate It is preferable to use an aprotic solvent such as potassium, butyl acetate, nitromethane, or nitrobenzene. In addition, it is recommended to use a polar solvent from the viewpoint of smoothly proceeding the fluorination reaction, and among the solvents exemplified above, valeronitrile, ethyl acetate, isopropyl acetate and butyl acetate are preferable. This is because by using these solvents, the by-product metal salt can be efficiently removed. From the viewpoint of workability during purification, a solvent having a low boiling point and capable of forming a two-layer state with water is preferable.

  The onium salt of di (fluorosulfonyl) imide or N- (fluorosulfonyl) -N- (fluoroalkylsulfonyl) imide represented by the above formula (III) becomes a room temperature molten salt that stably maintains a molten state at room temperature ( For example, it takes a liquid state at a temperature of 100 ° C. or lower), and is an ionic conductor material of an electrochemical device that can withstand long-term use, that is, an electrolyte that is dissolved in an electrolytic solution such as a lithium secondary battery, capacitor, or ionic liquid Useful.

Furthermore, the onium salt of fluorosulfonylimide represented by the above formula (III) can exchange the onium cation represented by R ⁵ in the formula (III) by reacting with an appropriate salt. Compound (VII) is obtained.

In the formula (VII), R ² is preferably an alkali metal such as Li, Na, K, Rb, Cs. More preferably, it is Li. R ⁴ represents fluorine or a fluorinated alkyl group having 1 to 6 carbon atoms, and 1 is 1. Alkali metal salts of di (fluorosulfonyl) imide and N- (fluorosulfonyl) -N- (fluoroalkylsulfonyl) imide, which are compounds (VII) obtained by the cation exchange reaction, also include lithium secondary batteries, capacitors, and ionicity. It is suitable as an electrolyte to be dissolved in an electrolytic solution such as a liquid.

Examples of the cation exchange reaction from compound (III) to compound (VII) include a method of reacting a salt containing a desired cation with compound (III), a method of contacting compound (III) with a cation exchange resin, and the like. It is done. Examples of the compound (salt) that gives the compound (VII) in which R ² is an alkali metal include hydroxides such as LiOH, NaOH, KOH, RbOH, CsOH, Na ₂ CO ₃ , K ₂ CO ₃ , Rb ₂ CO ₃ , Cs. ₂ carbonates such as CO ₃ , hydrides such as LiHCO ₃ , NaHCO ₃ , KHCO ₃ , RbHCO ₃ , CsHCO ₃ , chlorides such as LiCl, NaCl, KCl, RbCl, CsCl, LiF, NaF, KF, RbF, Examples include fluorides such as CsF, alkoxide compounds such as CH ₃ OLi, Et ₂ OLi, and alkyllithium compounds such as EtLi, BuLi, and t-BuLi (where Et represents an ethyl group and Bu represents a butyl group). .

  At this time, a solvent may be used as necessary. For example, ethylene carbonate, propylene carbonate, butylene carbonate, γ-butyrolactone, γ-valerolactone, dimethoxymethane, 1,2-dimethoxyethane, tetrahydrofuran, 2-methyl Tetrahydrofuran, 1,3-dioxane, 4-methyl-1,3-dioxolane, methyl formate, methyl acetate, methyl propionate, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, acetonitrile, sulfolane, 3-methyl sulfolane, dimethyl Sulfoxide, N, N-dimethylformamide, N-methyloxazolidinone, valeronitrile, benzonitrile, ethyl acetate, isopropyl acetate, butyl acetate, nitromethane, nitrobenzene, etc. These aprotic solvents are preferred. Among the solvents exemplified above, valeronitrile, ethyl acetate, isopropyl acetate and butyl acetate are preferable. This is because the reaction from the compound (I) to (III) and the reaction from the compound (III) to (VII) can be carried out in the same solvent without changing the solvent.

  The compounding ratio of compound (III) and alkali metal salt is preferably 1: 1 to 1:10 (compound (III): the above-mentioned salt, molar ratio). More preferably, it is 1: 1-1: 5, More preferably, it is 1: 1-1: 3.

  The reaction time and reaction temperature are not particularly limited, but it is recommended that the reaction time be 0 to 200 ° C. (more preferably 10 to 100 ° C.), 0.1 to 48 hours (more preferably 1 to 24 hours). The

  As the cation exchange resin, it is preferable to use a strongly acidic cation exchange resin. An example of the developing solvent is water.

  When using a cation exchange resin, first, the cation of the cation exchange resin is replaced with a desired cation by a known method, and then the aqueous solution of the above formula (III) dissolved in water is packed in a column. By passing the solution through the column, an aqueous solution containing the above formula (VII) exchanged with a desired cation can be obtained.

  Onium salts of fluorosulfonylimides such as di (fluorosulfonyl) imide and N- (fluorosulfonyl) -N- (fluoroalkylsulfonyl) imide obtained by the production method of the present invention are primary batteries and lithium (ion) secondary batteries. It is suitably used as a material for ion conductors constituting electrochemical devices such as batteries having a charge / discharge mechanism such as fuel cells, electrolytic capacitors, electric double layer capacitors, solar cells and electrochromic display elements. Further, alkali metal salts of fluorosulfonylimides and fluorosulfonylimides derived from onium salts of fluorosulfonylimides described above are electrolytes or intermediates thereof that are dissolved in an electrolytic solution such as a lithium secondary battery, a capacitor, or an ionic liquid. It is useful as such.

  When the di (fluorosulfonyl) imide salt or N- (fluorosulfonyl) -N- (fluoroalkylsulfonyl) imide salt according to the present invention is used as the electrolyte material, the electrolyte material further includes an alkali metal salt and Those comprising an alkaline earth metal salt are preferred. In this case, the alkali metal salt and / or alkaline earth metal salt is a compound having di (fluorosulfonyl) imide or N- (fluorosulfonyl) -N- (fluoroalkylsulfonyl) imide according to the present invention as an anion. It may be (a compound represented by the above formula (VII)) or a compound added separately. Since the electrolyte solution material containing such an alkali metal salt and / or alkaline earth metal salt contains an electrolyte, it is suitable as a material for an electrolyte solution of an electrochemical device. As the alkali metal salt, a lithium salt, a sodium salt, and a potassium salt are preferable, and as the alkaline earth metal salt, a calcium salt and a magnesium salt are preferable. More preferably, it is a lithium salt.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by the following examples as a matter of course, and appropriate modifications are made within a range that can meet the purpose described above and below. Of course, it is also possible to implement them, and they are all included in the technical scope of the present invention.

Synthesis Example 1 Synthesis of Chlorosulfonyl Isocyanate 80.1 g (1.0 mol) of liquid sulfuric anhydride (SO ₃ ) was placed in a 200 ml reaction vessel equipped with a stirrer, thermometer, reflux tube, and gas introduction tube. After introducing 61.5 g (0.53 mol) of cyanogen chloride (CNCl) at a temperature of 25 ° C. to 35 ° C. over 2 hours, the reaction solution was adjusted to 25 ° C. to 30 ° C. and stirred for 0.5 hour. did. After completion of the reaction, the reflux tube and the gas introduction tube were removed from the reaction vessel and distilled at normal pressure to obtain a colorless transparent liquid as a fraction of 106 ° C to 107 ° C (118.5 g, 0.83 mol, yield 83. 7%).

Synthesis Example 2 Synthesis of di (chlorosulfonyl) imide 148.7 g (1.28 mol) of chlorosulfonic acid (ClSO ₃ H) was added to a 500 ml reaction vessel equipped with a stirrer, thermometer, reflux tube, and dropping device. Heated to 120 ° C. Next, 180.4 g (1.27 mol) of chlorosulfonyl isocyanate obtained by the same method as in Synthesis Example 1 was added into the reaction vessel from the dropping device over 2 hours, and then the mixed solution was heated to 150 ° C. Stir for hours. After completion of the reaction, the reflux tube and the dropping device were removed from the reaction vessel, and vacuum distillation was performed to obtain a colorless and transparent liquid as a fraction at 104 to 106 ° C. (0.3 kPa) (yield: 178.4 g, 0 0.83 mol, yield 65.6%).

Identification was performed by IR (Varian 2000 FT-IR, manufactured by Varian, liquid film method), and confirmed to be di (chlorosulfonyl) imide.
IR (neat): ν _{s (NH)} 3155, ν _{as (SO)} 1433, 1428, ν _{s (SO)} 1183, ν _{s (NS)} 824 cm ⁻¹

Synthesis example 3
Synthesis Example 3-1 Synthesis of onium salt of chlorosulfonylimide 2.09 g (9.8 mmol) of di (chlorosulfonyl) imide obtained in Synthesis Example 2 and 4.2 g of butyl acetate were added to a 20 ml reaction vessel and stirred. did. Further, 0.99 g (9.8 mmol) of triethylamine was added thereto, followed by stirring at room temperature (25 ° C.) for 1 hour. The obtained reaction solution was analyzed with ¹ H-NMR (“Unity plus 400”, manufactured by Varian, internal standard substance: tetramethylsilane, cumulative number: 32 times), and triethylammonium di (chlorosulfonyl) imide was analyzed. It was confirmed that it was generated.
¹ H-NMR (CD ₃ CN): δ 3.1 (6H), 1.2 (t, 9H)

Synthesis Example 3-2 Synthesis of onium salt of fluorosulfonylimide To the solution of onium salt of chlorosulfonylimide obtained in Synthesis Example 3-1, 1.02 g (9.9 mmol) of ZnF ₂ was added, and room temperature (25 ° C.). The reaction was carried out for 3 hours. Thereafter, the reaction solution was transferred to a 100 ml separatory funnel, and 12.5 g of butyl acetate was added to dilute the reaction solution. Next, after adding and mixing 1.9 g of distilled water, a liquid separation operation for removing the aqueous phase was performed four times. The product was analyzed by ¹⁹ F-NMR (“Unity plus 400”, manufactured by Varian, internal standard substance: trifluoromethylbenzene, cumulative number: 32 times) and ¹ H-NMR (similar to Synthesis Example 3-1). As a result of measuring the peak area of the obtained chart and quantifying the conversion ratio from chlorine to fluorine, it was confirmed that triethylammonium di (fluorosulfonyl) imide was produced (yield: 1.83 g, 6 .5 mmol).
¹⁹ F-NMR (CD ₃ CN): δ 56.0
¹ H-NMR (CD ₃ CN): δ 3.1 (6H), 1.2 (9H)

Synthesis Example 3-3 Synthesis of Lithium Salt (Cation Exchange Reaction)
The solution containing triethylammonium di (fluorosulfonyl) imide obtained in Synthesis Example 3-2 was transferred to a 100 ml separatory funnel, and 0.82 g (19.5 mmol) of lithium hydroxide monohydrate was added to distilled water 4. An aqueous solution dissolved in 92 g was added and mixed. The aqueous phase was removed by a liquid separation operation. The same operation was repeated twice. The product was obtained by evaporating the solvent from the organic phase obtained to dryness. It was confirmed that lithium di (fluorosulfonyl) imide was produced by the disappearance of the triethylammonium-derived peak in ¹ H-NMR analysis. (Yield: 0.79 g, 4.2 mmol).

Synthesis example 4
Synthesis Example 4-1 Synthesis of onium salt of di (chlorosulfonyl) imide To a 50 ml reaction vessel, add 2.00 g (9.3 mmol) of di (chlorosulfonyl) imide obtained in Synthesis Example 2 and 18 g of valeronitrile. , Stirred. Triethylamine 0.95g (9.4mmol) was added here, and also it stirred. When the obtained reaction solution was analyzed by ¹ H-NMR, it was confirmed that triethylammonium di (chlorosulfonyl) imide was produced.
¹ H-NMR (CD ₃ CN): δ 3.1 (6H), 1.2 (9H)

Synthesis Example 4-2 Synthesis of onium salt of fluorosulfonylimide 0.97 g (9.4 mmol) of ZnF ₂ was added to the reaction solution obtained in Synthesis Example 4-1, and the reaction was performed at room temperature (25 ° C.) for 3 hours. It was. Thereafter, the reaction solution was transferred to a 100 ml separatory funnel, 1.9 g of water was added and mixed, and then the aqueous phase was removed by a liquid separation operation. This operation was performed 4 times, and the obtained organic phase was analyzed by ¹⁹ F-NMR and ¹ H-NMR to confirm that triethylammonium di (fluorosulfonyl) imide was produced (yield: 1.30 g, 4.6 mmol).
¹⁹ F-NMR (CD ₃ CN): δ 56.0
¹ H-NMR (CD ₃ CN): δ 3.1 (6H), 1.2 (9H)

Synthesis Example 4-3 Synthesis of Lithium Salt (Cation Exchange Reaction)
The organic phase obtained in Synthesis Example 4-2 was transferred to a 100 ml separatory funnel, and an aqueous solution in which 0.58 g (13.8 mmol) of lithium hydroxide monohydrate was dissolved in 3.5 g of distilled water was added and mixed. . Thereafter, the aqueous phase was removed by a liquid separation operation, and the solvent was evaporated from the obtained organic phase to dryness to obtain a product. ^The disappearance of the peak derived from triethylammonium in ¹ H-NMR analysis confirmed that lithium di (fluorosulfonyl) imide was produced (yield: 0.77 g, 4.1 mmol).
¹⁹ F-NMR (CD ₃ CN): δ 56.0

  From the results of Synthesis Examples 3 and 4, it can be seen that according to the method of the present invention, chlorosulfonylimide can be efficiently fluorinated by using a fluorinating agent that is less expensive than conventional methods. Further, the method of the present invention is excellent in workability because the fluorination and the cation exchange reaction can be carried out in the same reaction solvent and the purification can be performed only by a liquid separation operation.

Comparative Synthesis Example 1 Synthesis of di (fluorosulfonyl) imide To a 20 ml reaction vessel, 3.09 g (14.4 mmol) of di (chlorosulfonyl) imide and 6.18 g of acetonitrile were added and stirred. To this, 3.57 g (61.5 mmol) of potassium fluoride was added, and the reaction was performed at room temperature (25 ° C.) for 24 hours. The reaction solution was filtered, and the filtrate was washed with 5 g of acetonitrile, and the combined solution of the filtrate and the washing solution was analyzed by ¹⁹ F-NMR in the same manner as in Synthesis Example 3. As a result, the conversion rate from chlorine to fluorine was It was confirmed that most of the raw material was not fluorinated and remained di (chlorosulfonyl) imide.
¹⁹ F-NMR (CD ₃ CN): δ 55.9

Synthesis Example 5 Synthesis of N- (chlorosulfonyl) -N- (trifluoromethylsulfonyl) imide A trifluoromethanesulfonic acid (CF ₃ SO ₃₎ was added to a 500 ml reaction vessel equipped with a stirrer, a thermometer, a reflux tube and a dropping device. H) 190.6 g (1.27 mol) was added and heated to 120 ° C. Next, 179.7 g (1.27 mol) of chlorosulfonyl isocyanate obtained by the same method as in Synthesis Example 1 was added into the reaction vessel from the dropping device over 2 hours, and then the mixed solution was heated to 150 ° C. Stir for hours. After completion of the reaction, the reflux tube and the dropping device were removed from the reaction vessel, and vacuum distillation was performed to obtain a colorless and transparent liquid (yield: 212.9 g, 0.86 mol, yield 67.7%).

^The product was confirmed to be N- (chlorosulfonyl) -N- (trifluoromethylsulfonyl) imide by ¹⁹ F-NMR measurement.

Synthesis Example 6
Synthesis Example 6-1 Synthesis of Onium Salt In a 50 ml reaction vessel, 2.00 g (8.1 mmol) of N-chlorosulfonyl-N- (trifluoromethylsulfonyl) imide obtained in Synthesis Example 5 and 18 g of butyl acetate were added. Added and stirred. Triethylamine 0.82g (8.1mmol) was added here, and it stirred at room temperature (25 degreeC) for 1 hour. The obtained reaction solution was analyzed by ¹ H-NMR, and it was confirmed that triethylammonium N- (chlorosulfonyl) -N- (trifluoromethylsulfonyl) imide was produced.
¹ H-NMR (CD ₃ CN): δ 3.1 (6H), 1.2 (9H)

Synthesis Example 6-2 Synthesis of onium salt of fluorosulfonylimide 0.88 g (8.5 mmol) of ZnF ₂ was added to the reaction solution obtained in Synthesis Example 6-1 and reacted at room temperature (25 ° C.) for 3 hours. . Thereafter, the reaction solution was transferred to a 100 ml separatory funnel, 1.9 g of water was added and mixed, and then a liquid separation operation for removing the aqueous phase was performed four times. The obtained reaction solution was analyzed by ¹⁹ F-NMR and ¹ H-NMR, and it was confirmed that triethylammonium-N- (fluorosulfonyl) -N- (trifluoromethylsulfonyl) imide was produced (yield: 1.63 g, 4.9 mmol).
¹ H-NMR (CD ₃ CN): δ 3.1 (6H), 1.2 (9H)

Synthesis example 7
Synthesis Example 7-1 Synthesis of Onium Salt To a 50 ml reaction vessel, 2.00 g (9.3 mmol) of di (chlorosulfonyl) imide obtained in Synthesis Example 2 and 18 g of butyl acetate were added and stirred. Further, 0.94 g (9.3 mmol) of triethylamine was added thereto and stirred. The obtained reaction solution was analyzed by ¹ H-NMR, and it was confirmed that triethylammonium di (chlorosulfonyl) imide was produced (yield: 1.47 g, 5.2 mmol).
¹ H-NMR (CD ₃ CN): δ 3.1 (6H), 1.2 (9H)

Synthesis Example 7-2 Synthesis of Onium Salt of Fluorosulfonylimide Next, 1.00 g (0.98 mmol) of CuF ₂ was added to the reaction solution obtained in Synthesis Example 7-1 and reacted at room temperature (25 ° C.) for 3 hours. Went.

Thereafter, the reaction solution was transferred to a 100 ml separatory funnel, and 1.9 g of distilled water was added thereto and mixed, and then a liquid separation operation for removing the aqueous phase was performed four times. Butyl acetate was distilled off from the obtained organic phase to obtain an oily yellow product. The product was analyzed by ¹⁹ F-NMR and ¹ H-NMR, and it was confirmed that triethylammonium di (fluorosulfonyl) imide was produced (yield: 1.47 g, 5.2 mmol).
¹⁹ F-NMR (CD ₃ CN): δ 56.0
¹ H-NMR (CD ₃ CN): δ 3.1 (6H), 1.2 (9H)

Synthesis Example 8
Synthesis Example 8-1 Synthesis of Onium Salt To a 50 ml reaction vessel, 2.00 g (9.3 mmol) of di (chlorosulfonyl) imide and 18 g of butyl acetate were added and stirred. Triethylamine 0.94g (9.3mmol) was added here, and it stirred. When the obtained reaction solution was analyzed by ¹ H-NMR, it was confirmed that triethylammonium di (chlorosulfonyl) imide was produced.

Synthesis Example 8-2 Synthesis of onium salt of fluorosulfonylimide 1.66 g (6.2 mmol) of BiF ₃ was added to the reaction solution obtained in Synthesis Example 8-1, and the reaction was performed at room temperature (25 ° C.) for 3 hours. It was.

Thereafter, the reaction solution was transferred to a 100 ml separatory funnel, 1.9 g of distilled water was added and mixed, and then a liquid separation operation for removing the aqueous phase was performed four times. The obtained organic phase was analyzed by ¹⁹ F-NMR and ¹ H-NMR, and it was confirmed that triethylammonium di (fluorosulfonyl) imide was produced (yield: 1.36 g, 4.8 mmol).
¹⁹ F-NMR (CD ₃ CN): δ 56.0
¹ H-NMR (CD ₃ CN): δ 3.1 (6H), 1.2 (9H)

  From the results of Synthesis Examples 7 and 8, even when a fluoride having an element other than Zn in Groups 11 to 15 and Periods 4 to 6 (excluding arsenic and antimony) is used. It can be seen that fluorination of chlorosulfonylimide proceeds promptly and efficiently, and fluorosulfonylimides can be obtained without generating by-products.

Synthesis Example 9 Synthesis of Lithium Salt 1688 g of a solution prepared by dissolving triethylammonium di (fluorosulfonyl) imide obtained in the same manner as in Synthesis Example 3-2 in butyl acetate to a concentration of 7.7% (0 .46 mol) was added to a 3 L separatory funnel. To this, 58 g (1.38 mol) of lithium hydroxide dissolved in 348 g of ultrapure water was added and mixed, and then the aqueous phase was removed. The formation of the target product was confirmed by the disappearance of the peak derived from triethylammonium by ¹⁹ F-NMR and ¹ H-NMR analyses.

  Subsequently, the reaction solution was dried under reduced pressure at 50 ° C. to obtain 80 g (0.43 mol) of lithium di (fluorosulfonyl) imide.

Synthesis Example 10 Synthesis of di (chlorosulfonyl) imide 48.5 g (0.5 mol) of amidosulfuric acid, 178.5 g of thionyl chloride and chlorosulfonic acid were added to a 500 ml reaction vessel equipped with a stirrer, thermometer and reflux tube. The mixed solution was reacted under stirring at 70 ° C. for 4 hours and at 130 ° C. for 20 hours. After completion of the reaction, the reflux tube was removed from the reaction vessel and vacuum distillation was performed to obtain a colorless and transparent liquid as a fraction at 104 ° C to 105 ° C (yield: 102.7 g, 0.48 mol, yield 96%). .

Identification was performed by IR (Varian 2000 FT-IR, manufactured by Varian, liquid film method), and confirmed to be di (chlorosulfonyl) imide.
IR (neat): ν _{s (NH)} 3155, ν _{as (SO)} 1433, 1428, ν _{s (SO)} 1183, ν _{s (NS)} 824 cm ⁻¹

Synthesis Example 11
Synthesis Example 11-1 Synthesis of onium salt of chlorosulfonylimide 2.09 g (9.8 mmol) of di (chlorosulfonyl) imide obtained in Synthesis Example 2 and 4.2 g of butyl acetate were added to a 20 ml reaction vessel and stirred. did. Further, 1.35 g (9.8 mmol) of triethylamine hydrochloride was added thereto, followed by stirring at room temperature (25 ° C.) for 1 hour. The obtained reaction solution was subjected to the same conditional ¹ H-NMR analysis as in Synthesis Example 3-1, and it was confirmed that triethylammonium di (chlorosulfonyl) imide was produced.
¹ H-NMR (CD ₃ CN): δ 3.1 (6H), 1.2 (9H)

Synthesis Example 11-2 Synthesis of onium salt of fluorosulfonylimide To the solution of onium salt of chlorosulfonylimide obtained in Synthesis Example 11-1, 1.02 g (9.9 mmol) of ZnF ₂ was added, and room temperature (25 ° C.). The reaction was carried out for 3 hours. Thereafter, the reaction solution was transferred to a 100 ml separatory funnel, and 12.5 g of butyl acetate was added to dilute the reaction solution. Next, after adding and mixing 1.9 g of distilled water, a liquid separation operation for removing the aqueous phase was performed four times. The product is subjected to ¹⁹ F-NMR and ¹ H-NMR (similar to Synthesis Example 3-1) analysis under the same conditions as in Synthesis Example 3-2, and the peak area of the obtained chart is measured. From chlorine to fluorine As a result of quantifying the conversion ratio, it was confirmed that triethylammonium di (fluorosulfonyl) imide was produced (yield: 1.82 g, 6.4 mmol).
¹⁹ F-NMR (CD ₃ CN): δ 56.0

  According to the present invention, since the fluorination reaction is performed after chlorosulfonylimide is converted to an onium salt, heat generation is suppressed, and the fluorination reaction can proceed more safely. In addition, by appropriately selecting the reaction solvent, the metal salt produced by the fluorination reaction can be easily removed and the solvent can be efficiently removed, so that the workability of the purification process is improved. Furthermore, according to the present invention, the production of by-products can be suppressed without using expensive fluorinating agents such as antimony (Sb) and arsenic (As), which is more efficient than conventional methods. Often, N- (fluorosulfonyl) -N- (fluoroalkylsulfonyl) imide, di (fluorosulfonyl) imide and organic salts and metal salts thereof are obtained. In addition, fluorosulfonylimides obtained by the method of the present invention include primary batteries, batteries having a charge / discharge mechanism such as lithium (ion) secondary batteries and fuel cells, electrolytic capacitors, electric double layer capacitors, solar cells / electrochromics. It is considered that it is suitably used as a material for an ion conductor constituting an electrochemical device such as a display element.

Claims (5)

A method for producing a fluorosulfonylimide salt represented by the following scheme,
A step of obtaining a chlorosulfonylimide onium salt represented by the general formula (II) by reacting a compound represented by the general formula (I) with an onium salt in the following scheme;
A fluoride containing at least one element selected from the group consisting of onium salts of chlorosulfonylimide and elements of Groups 11 to 15 and Groups 4 to 6 (excluding arsenic and antimony) And a step of obtaining a compound represented by the general formula (III),
In this order, a method for producing a fluorosulfonylimide salt.
In the above scheme, R ³ is fluorine, chlorine or a fluorinated alkyl group having 1 to 6 carbon atoms, R ⁴ is fluorine or a fluorinated alkyl group having 1 to 6 carbon atoms, R ⁵ is an onium cation, n Corresponds to the valence of the onium cation R ⁵ and represents an integer of 1 to 3.   The method for producing a fluorosulfonylimide salt according to claim 1, wherein the fluoride contains at least one element selected from the group consisting of Cu, Zn, and Bi.   The method for producing a fluorosulfonylimide salt according to claim 1 or 2, wherein the compound represented by the general formula (I) is obtained using cyanogen chloride as a starting material.   The method for producing a fluorosulfonylimide salt according to claim 1 or 2, wherein the compound represented by the general formula (I) is obtained using amidosulfuric acid as a starting material. A compound represented by the following general formula (VII) obtained by further reacting the compound represented by the general formula (III) obtained by the method according to any one of claims 1 to 4 with an alkali metal salt. The manufacturing method of the fluoro sulfonylimide salt in any one of Claims 1-4 including the process of obtaining.

In the formula (VII), R ² represents an alkali metal, R ⁴ represents fluorine or a fluorinated alkyl group having 1 to 6 carbon atoms, and 1 is 1.