KR101925482B1 - Method for producing (fluorosulfonyl)perfluoroalkanesulfonylimide salt - Google Patents

Abstract

(Fluorosulfonyl) perfluoroalkanesulfonylimide salt at a high selectivity and a high yield.
The perfluoroalkanesulfonyl halide is reacted with ammonia in a solvent to obtain a solution containing an ammonium salt of perfluoroalkanesulfonamide and an ammonium halide (first step), and the resultant solution is subjected to filtration to obtain a solution (The second step), and adding a perfluoroalkanesulfonamide ammonium salt to the resulting solution containing an ammonium salt of an organic base by adding an organic base to the solution containing the perfluoroalkanesulfonamide ammonium salt and ammonia Perfluoroalkanesulfonylimide salt is prepared by obtaining a solution (third step) by adding sulfolyl fluoride to the obtained solution (fourth step), thereby preparing a (fluorosulfonyl) perfluoroalkanesulfonylimide salt.

Description

(METHOD FOR PRODUCING (FLUOROSULFONYL) PERFLUOROALKANESULFONYLIMIDE SALT} [0001] This invention relates to a process for producing (fluorosulfonyl) perfluoroalkanesulfonylimide salt,

The present invention relates to a process for the preparation of (fluorosulfonyl) perfluoroalkanesulfonylimide salts.

(Fluorosulfonyl) perfluoroalkanesulfonylimide salt is also useful as a solvent for a battery electrolyte, an acid catalyst, an ionic liquid or an antistatic agent.

(Fluorosulfonyl) perfluoroalkanesulfonyl imide, there is a method of reacting perfluoroalkanesulfonamide with sulfuryl fluoride (Patent Document 1), a method of reacting perfluoroalkanesulfonamide with perfluoroalkanesulfonamide (Patent Document 2), a method of reacting perfluoroalkanesulfonamide with fluorosulfuric acid and thionyl chloride (Patent Document 3), a method of reacting perfluoroalkane isocyanate with sulfur trioxide , And a method of reacting an ammonium fluoride salt (Patent Document 4).

[Chemical Formula 1]

U.S. Patent No. 5874616 Specification International Publication No. 2011/148961 International Publication No. 2011/148958 Japanese Unexamined Patent Application Publication No. 2012-162470

Although the method of Patent Document 1 is a preferable method, the yield was low to medium (55%), and it was not always efficient.

In the methods of Patent Document 2 and Patent Document 3, since the reaction liquid becomes acidic due to by-product sulfuric acid or hydrochloric acid, and there is a possibility that the (fluorosulfonyl) perfluoroalkanesulfonylimide is decomposed, Could not.

In addition, since the methods of Patent Document 2, Patent Document 3 and Patent Document 4 use fluorosulfuric acid which is highly toxic or sulfur trioxide which is dangerous to handle, it is difficult to adopt it as an industrial production method.

Therefore, the inventors of the present invention have made extensive studies in view of the above-mentioned problems. As a result, it has been found that perfluoroalkanesulfonamide is generated in a reaction solution to remove ammonium fluoride from the by-product and the obtained solution is reacted with an organic base and sulfuryl fluoride (Fluorosulfonyl) perfluoroalkanesulfonylimide salt. Thus, the present invention has been completed.

That is, the present invention provides the invention described in [Invention 1] - [Invention 6] below.

[Invention 1]

Equation [1]:

(2)

_Wherein R _f represents a linear or branched perfluoroalkyl group having 1 to 6 carbon atoms and B represents an organic base,

A process for producing a (fluorosulfonyl) perfluoroalkanesulfonylimide salt represented by the general formula (1), comprising the following steps:

[First Step]

Equation [2]:

(3)

_Wherein R _f represents a linear or branched perfluoroalkyl group having 1 to 6 carbon atoms and X represents a halogen atom,

(NH ₃ ) in the presence of a solvent to obtain a solution containing an ammonium salt of perfluoroalkanesulfonamide and an ammonium halide, by reacting perfluoroalkanesulfonyl halide represented by the general formula

[Second Step]

A step of separating and removing the ammonium halide contained in the solution by filtering (separately) the solution obtained in the first step to obtain a solution containing an ammonium perfluoroalkanesulfonamide salt.

[Third Step]

To the solution containing the perfluoroalkanesulfonamide ammonium salt obtained in the second step, an organic base was added to obtain a solution containing the " salt of perfluoroalkanesulfonamide and organic base " and ammonia, And separating and removing ammonia from the solution.

[Fourth Step]

(Fluorosulfonyl) purple in the presence of an organic base with respect to a solution containing " a salt of a perfluoroalkanesulfonamide and a salt of an organic base " obtained by separating and removing ammonia in a third step A process for obtaining a fluoroalkanesulfonylimide salt.

[Invention 2]

The process according to claim 1, wherein in the first step, the solvent is acetonitrile, propionitrile, dimethylsulfoxide, sultone, diglyme, tetrahydrofuran or dimethylformamide.

[Invention 3]

The production method according to claim 1 or 2, wherein the reaction temperature in the first step is 0 占 폚 to 100 占 폚.

[Invention 4]

The production method according to claim 1, wherein the temperature at the time of separation is 10 占 폚 to 80 占 폚 in the second step.

[Invention 5]

In the third step, when separating and removing ammonia from the solution containing a solution containing "perfluoroalkanesulfonamide and a salt of an organic base" and ammonia under a pressure of 0.02 MPa to 0.1 MPa at 20 ° C To 80 < 0 > C.

[Invention 6]

(Fluorosulfonyl) perfluoroalkanesulfonylimide salt was prepared in any one of the inventions 1 to 5, and then the resulting (fluorosulfonyl) perfluoroalkanesulfonylimide salt was reacted with a hydroxide of an alkali metal Or a carbonate or a hydroxide or carbonate of an alkaline earth metal,

[Chemical Formula 4]

[In the formula [3], R _f is the same as the formula [1] of the invention 1. M represents an alkali metal or an alkaline earth metal. and n represents an integer of the same number as the valence of the corresponding metal.

(Fluorosulfonyl) perfluoroalkanesulfonylimidic acid metal salt represented by the formula (I).

The present invention is characterized in particular by combining the second process. When the third step and the fourth step are subsequently carried out under the condition that the second step is not carried out, ammonium halide is included in the reaction system. When the fourth step, which is the final step of the present invention, is carried out under these conditions, bis-fluorosulfonylimide, which is a by-product, is produced, and the desired product, (fluorosulfonyl) perfluoroalkanesulfonylimide salt, (See comparative example to be described later).

Therefore, the present inventors have found that the ammonium halide contained in the solution is separated and removed by filtration of the solution obtained in the first step (Step 2), and then an organic base is added to the filtrate obtained in the second step ) Was prepared by reacting the resulting salt with "perfluoroalkanesulfonamide and a salt of an organic base", and reacting sulfuryl fluoride with the obtained salt (fourth step) to obtain the target product (fluorosulfonyl) perfluoroalkane Sulfonylimide salt can be obtained in high yield.

Further, the (fluorosulfonyl) perfluoroalkanesulfonylimide salt can be easily produced by reacting a hydroxide of an alkali metal or a hydroxide of an alkaline earth metal to easily produce a (fluorosulfonyl) perfluoro It was also found that this compound can be derived as a metal salt of haloalkanesulfonyl imidic acid.

The present invention relates to a process for producing (fluorosulfonyl) perfluoroalkanesulfonylimide salt, which is an objective product, without isolating a perfluoroalkanesulfonamide salt as an intermediate, The organic solvent used can be used without being removed to the fourth step as it is, and it can be said to be a very advantageous method which is easy to adopt as an industrial production method.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to produce an industrially advantageous (fluorosulfonyl) perfluoroalkanesulfonylimide salt with little waste, without isolating the perfluoroalkanesulfonamide from each step .

Hereinafter, the present invention will be described in detail. Hereinafter, the embodiments of the present invention will be described. However, the present invention is not limited to the following embodiments, but may be appropriately carried out in accordance with the ordinary knowledge of a person skilled in the art have.

The present invention relates to a process for producing a (fluorosulfonyl) perfluoroalkanesulfonylimide salt, wherein perfluoroalkanesulfonyl halide is reacted with ammonia in a solvent to produce a perfluoroalkanesulfonamideimide salt and an ammonium halide (First step), and then the solution obtained in the first step is subjected to separation to separate and remove the ammonium halide contained in the solution to obtain a solution containing the perfluoroalkanesulfonamide ammonium salt (The second step), and then by adding an organic base to a solution containing the perfluoroalkanesulfonamide ammonium salt obtained in the second step, "a salt of a perfluoroalkanesulfonamide and an organic base" and ammonia , Followed by separating and removing ammonia from the solution (third step), and subsequently adding the solution obtained in the third step (Fourth step) of obtaining a (fluorosulfonyl) perfluoroalkanesulfonylimide salt by adding sulfuryl fluoride in the presence of an organic base.

Subsequently, by reacting a (fluorosulfonyl) perfluoroalkanesulfonylimide salt prepared by the methods of the first to fourth processes with a hydroxide of an alkali metal or a hydroxide of an alkaline earth metal, (Fluorosulfonyl) perfluoroalkanesulfonylimidic acid metal salt of the present invention will be described in detail below.

<First Step>

First, the first step will be described. The first step is a step of reacting perfluoroalkanesulfonyl halide with ammonia (NH ₃ ) in the presence of a solvent to obtain a solution containing an ammonium salt of perfluoroalkanesulfonamide and an ammonium halide (scheme ) One).

[Chemical Formula 5]

The perfluoroalkanesulfonyl halide used in the present step is a straight-chain or branched perfluoroalkanesulfonyl halide having 1 to 6 carbon atoms, but preferably has 1 to 4 carbon atoms, more preferably 1 (trifluoromethyl) Is particularly preferable. Specific examples of the compound include trifluoromethanesulfonyl fluoride, pentafluoroethanesulfonyl fluoride, heptafluoropropanesulfonyl fluoride, nonafluorobutane sulfonyl fluoride, trifluoromethanesulfonyl chloride, pentafluoro Heptafluoropropane sulfonyl chloride, nonafluorobutane sulfonyl chloride, trifluoromethanesulfonyl bromide, pentafluoroethanesulfonyl bromide, heptafluoropropanesulfonyl bromide, nonafluorobutane bromide, heptafluoropropane sulfonyl chloride, There may be mentioned sulfonyl bromide, trifluoromethanesulfonyliodide, pentafluoroethanesulfonyliodide, heptafluoropropanesulfonyliodide, nonafluorobutanesulfonyliodide, and the like.

Of these, trifluoromethanesulfonyl fluoride, pentafluoroethanesulfonyl fluoride, heptafluoropropanesulfonyl fluoride, trifluoromethanesulfonyl chloride, pentafluoroethanesulfonyl chloride, heptafluoropropane But are not limited to, sulfonyl chloride, trifluoromethanesulfonyl bromide, pentafluoroethanesulfonyl bromide, heptafluoropropanesulfonyl bromide, trifluoromethanesulfonyliodide, pentafluoroethanesulfonyliodide, heptafluoropropane Sulfonyl iodide is preferable, and trifluoromethanesulfonyl fluoride, pentafluoroethanesulfonyl fluoride, trifluoromethanesulfonyl chloride, pentafluoroethanesulfonyl chloride, trifluoromethanesulfonyl bromide, trifluoromethanesulfonyl bromide, Pentafluoroethanesulfonyl bromide, trifluoromethanesulfonyl iodine Particularly preferred is pentafluoroethanesulfonyliodide (Scheme 1).

The amount of ammonia to be used in the present step is 3 molar in terms of stoichiometric amount relative to 1 mol of the perfluoroalkanesulfonyl halide, and is usually 3 to 10 mol, preferably 3 to 5 mol, . If it is less than 3 moles, the reaction yield may be decreased. There is no problem in the progress of the reaction even if the molar ratio exceeds 10 mol, but there is no particular advantage in terms of reaction rate, yield, or economy. The ammonia used in the present step can be used in its own, alone (NH ₃ ; anhydrous ammonia), or dissolved in a solvent such as water (ammonia water, etc.).

As the solvent used in this step, a polar solvent which does not react with ammonia or a perfluoroalkanesulfonyl halide is usually used, but a polar solvent such as acetonitrile, propionitrile, dimethylsulfoxide, sultone, diglyme, tetrahydrofuran, dimethylformamide And a nitrile-based solvent such as acetonitrile or propionitrile is particularly preferable.

The amount of the solvent to be used is not particularly limited and may be 0.1 L or more, preferably 0.1 to 20 L, and more preferably 0.1 to 10 L, per mole of the perfluoroalkanesulfonyl halide.

The temperature condition is not particularly limited, but it may be performed in a range of -50 to 200 캜. The temperature is usually 0 to 100 占 폚, more preferably 0 to 70 占 폚.

When the temperature is lower than -50 占 폚, the reaction rate is lowered, and when the temperature is higher than 200 占 폚, product decomposition may occur.

The pressure conditions are not particularly limited and may be, for example, in a range of from 0.02 MPa to 3 MPa (absolute pressure: the same applies hereinafter)). In this case, 0.02 MPa to 2 MPa is preferable, and 0.02 MPa to 1 MPa is more preferable.

Examples of the reaction vessel used for the reaction include monel, Hastelloy, nickel, or an internal pressure reaction vessel lined with a fluorine resin such as polytetrafluoroethylene or perfluoropolyether resin.

The reaction time is not particularly limited, but may be in the range of 0.1 to 24 hours. Since the reaction time varies depending on the substrate and the reaction conditions, the progress of the reaction can be controlled by means of gas chromatography, liquid chromatography, It is preferable to use the point where the perfluoroalkanesulfonyl halide is almost lost as the end point although it is the raw material.

In this step, ammonium halide (NH ₄ · X) is also produced in the reaction system at the same time as the production of the perfluoroalkanesulfonamide ammonium salt, so that after the reaction, it is obtained as a solution containing the target ammonium salt, ammonium halide and solvent . It is one of the preferable embodiments from the viewpoint of productivity that the object is not isolated from the solution but used as a raw material for the second step as it is.

&Lt; Second Step &

Next, the second step will be described. In the second step, the solution obtained in the first step is separated to remove the ammonium halide contained in the solution to obtain a solution containing the perfluoroalkanesulfonamide ammonium salt (Scheme 2).

[Chemical Formula 6]

As the embodiment for carrying out the sorption (also referred to as filtration), there is no particular limitation and it may be carried out as a normal operation of organic chemistry. For example, centrifugation, vacuum filtration, and pressure filtration are preferable, and centrifugation and pressure filtration are particularly preferable.

The temperature under which the filtration is carried out is preferably from 10 to 80 캜, and particularly preferably from 30 to 60 캜. If the temperature is lower than 10 占 폚, the perfluoroalkanesulfonamide ammonium salt is also precipitated and the yield is lowered. Further, at a temperature exceeding 80 캜, the ammonium halide dissolves in the solvent, which makes it difficult to separate it, which causes the selectivity and yield of the object to be reduced in the fourth step to be described later.

After this step, a solution containing the ammonium salt of perfluoroalkanesulfonamide in which the ammonium halide has been separated and removed is obtained, but this solution can be used as the raw material for the third step as it is without carrying out the purification operation at this stage.

<Third Step>

Next, the third step will be described. In the third step, a solution containing perfluoroalkanesulfonamide and organic base salt and ammonia is added to a solution containing the perfluoroalkanesulfonamide ammonium salt obtained in the second step by adding an organic base , Followed by separation and removal of ammonia from the solution (Scheme 3).

(7)

The organic base used in the present invention is preferably an organic base selected from the group consisting of methylamine, dimethylamine, ethylamine, diethylamine, n-propylamine, di-n-propylamine, i-propylamine, diisopropylamine, butylamine, di-sec-butylamine, tert-butylamine, di-tert-butylamine, phenylamine or diphenylamine, or a secondary amine,

The following formula

[Chemical Formula 8]

Wherein R ¹ , R ² and R ³ are the same or different and each represents a linear or branched alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or an aryl group (I), a halogen atom (fluorine, chlorine, bromine, iodine), an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, Or may be substituted by an actual group).

A tertiary amine represented by the general formula

Pyridine, pyrazine, pyrazine, oxazole, isoxazole, thiazole, isothiazole, imidazole, 1,2-dimethylpyridine, 2,4,6-trimethylpyridine, 4-dimethylaminopyridine, lutidine, Imidazole, imidazole, 3- (dimethylamino) propylimidazole, pyrazole, furazan, quinoline, isoquinoline, purine, 1H-indazole, quinazoline, cinnoline, quinoxaline, phthalazine, Di-t-butylpyridine, 2,2'-bipyridine, 4,4'-dimethyl-2,2'-bipyridyl, 4,4'-dimethyl- -Bipyridyl, 5,5'-dimethyl-2,2'-bipyridyl, 6,6'-t-butyl-2,2'-dipyridyl, 4,4'- '-Bipyridyl, 1,10-phenanthroline, 2,7-dimethyl-1,10-phenanthroline, 5,6-dimethyl-1,10-phenanthroline, 4,7- , Nitrogen-containing aromatic heterocyclic compounds such as 10-phenanthroline,

An imine base such as 1,8-diazabicyclo [5.4.0] undeca-7-ene, 1,5-diazabicyclo [4.3.0]

.

Specific examples of the tertiary amine include trimethylamine, triethylamine, N-ethyldiisopropylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, trioctylamine, Amine, triphenylamine, tribenzylamine, tris (2-ethylhexyl) amine, N, N-dimethyldecylamine, N-benzyldimethylamine, N-butyldimethylamine, N, N-dimethylcyclohexylamine, N, N ', N'-tetramethylethylenediamine, N, N-dimethylaniline, N, N-diethylaniline, 1,4-diazabicyclo [2.2.2] octane, N-methylpyrrolidine, N Methylpiperidine, N-methylmorpholine, N-ethylmorpholine, N, N'-dimethylpiperazine, N-methylpiperolin, N-methylpyrrolidone, N- N, N ', N''-pentamethyldiethylenetriamine, triethanolamine, tripropanolamine, dimethylethanolamine, dimethylaminoethoxyethanol, N, N' - dimethylaminopropylamine, N, N, N ' , N ', N' '- pentamethyldipropylenetriamine, tris (3-dimethylaminopropyl) amine, tetramethylimino-bis (propylamine), N, N-diethyl-ethanolamine and the like.

Among them, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diphenylamine, trimethylamine, triethylamine, diisopropylethylamine, Amine, tri-n-butylamine, pyridine, 2,4,6-trimethylpyridine, 4-dimethylaminopyridine, lutidine, pyrimidine, pyridazine, pyrazine, 1,8-diazabicyclo [5.4.0] 7-ene is preferable, and diethylamine, triethylamine, diisopropylethylamine, tri-n-butylamine and pyridine are more preferable.

The amount of the organic base to be used in the present step is usually 1 mol or more per 1 mol of the perfluoroalkanesulfonamide ammonium salt. In order to smoothly carry out the present process, it is necessary to stoichiometrically 1 mole of the organic base per 1 mole of the perfluoroalkanesulfonamide ammonium salt, but also in the fourth step which will be described later, the "perfluoroalkanesulfonamide and the salt of the organic base" And sulfuryl fluoride are reacted, one mole of the organic base is required per mole of the salt. Therefore, in the present step, the organic base may be used in an amount of 2 moles or more per 1 mole of the perfluoroalkanesulfonamide ammonium salt, assuming the fourth step to be described later.

If the amount of the organic base is less than 1 mole, the ammonia can not be released (liberated) sufficiently. In addition, when the organic base is used in a stoichiometric amount or more, the reaction rate is increased and the time of the third step can be shortened, but if it is used excessively more than necessary, it is economically disadvantageous. Therefore, the amount of the organic base to be used is preferably 2 to 10 moles, more preferably 2.5 to 5 moles per mole of the perfluoroalkanesulfonamide ammonium salt.

Since ammonia is generated in the reaction system as the reaction proceeds by adding an organic base, in this step, for example, a method of reacting with a reaction vessel equipped with a cooler and recovering ammonia generated with the progress of the reaction by a cooler . The method is not particularly limited and can be appropriately adjusted by those skilled in the art.

Further, when ammonia is recovered, it is possible to efficiently recover ammonia by employing the reaction conditions (temperature condition, pressure condition) described later.

The reaction temperature is usually from 20 to 80 캜, preferably from 25 to 60 캜. If the reaction temperature is lower than 20 ° C, the free glass of ammonia is not sufficiently removed and the time required for the process becomes long. On the other hand, in the case of a reaction temperature exceeding 80 캜, the solvent or the organic base may be scattered.

The pressure conditions are usually 0.02 MPa to 0.1 MPa, preferably 0.04 MPa to 0.08 MPa. However, if the decompression degree is too large, the solvent or the organic base may be scattered, which is economically disadvantageous.

In the present step, ammonia is separated and removed from the solution containing the "perfluoroalkanesulfonamide and the salt of an organic base" and ammonia (NH ₃ ) under the pressure condition of 0.02 MPa to 0.1 MPa , And heating at 20 캜 to 80 캜 is one of preferred embodiments.

The reaction time is not particularly limited, but may be in the range of 0.1 to 24 hours. Since the reaction time differs depending on the substrate and the reaction conditions, the reaction time can be determined by analyzing means such as gas chromatography, liquid chromatography, ion chromatography, And it is preferable that the point of time when the perfluoroalkanesulfonamide ammonium salt is almost lost is the end point.

In the fourth step, a side reaction occurs when the ammonium salt is reacted with sulfuryl fluoride in a state in which a large amount of the ammonium salt remains in the reaction solution, and the yield of the target product in the fourth step is lowered. Therefore, unreacted perfluoroalkane It is preferable that the sulfonamide ammonium salt is small.

Examples of the reaction vessel used for the reaction include monel, Hastelloy, nickel, or an internal pressure reaction vessel lined with a fluorine resin such as polytetrafluoroethylene or perfluoropolyether resin.

Thus, in the present step, by converting the perfluoroalkanesulfonamide ammonium salt (R _f SO ₂ NH ₂ .NH ₃ ) into a salt of the perfluoroalkanesulfonamide with an organic base and performing the reaction under specific reaction conditions, Can be removed.

In addition, the use of the solution containing the "perfluoroalkanesulfonamide and the salt of an organic base" obtained in the present step as a raw material for the fourth step as it is, is one of preferable embodiments from the viewpoint of productivity.

&Lt; Fourth step &

Next, the fourth step will be described. In the fourth step, sulfuryl fluoride is added to a solution containing the "perfluoroalkanesulfonamide and a salt of an organic base" obtained in the third step in the presence of an organic base to obtain (fluorosulfonyl) perfluoroalkane (Scheme 4). &Lt; / RTI &gt;

[Chemical Formula 9]

The amount of the sulfuryl fluoride used in the present step is usually 1 mole or more in terms of stoichiometric amount of 1 mole per mole of "perfluoroalkanesulfonamide and organic base salt". However, in practice, it is appropriately selected from 1 mole to 10 moles, preferably 1 to 5 moles.

If it is less than 1 mole, the reaction yield may be decreased. There is no problem in the progress of the reaction even if the molar ratio exceeds 10 mol, but there is no particular advantage in terms of reaction rate, yield, or economy.

Regarding the organic base, the same kind as that used in the third step can be separately added to the present step. The amount of the organic base to be used is usually 1 mole in terms of the stoichiometric amount per mole of the "perfluoroalkanesulfonamide and the salt of the organic base". However, as described in the third step, in the third step, When an organic base is used in a stoichiometric amount or more (specifically, when 2 moles or more per mole of perfluoroalkanesulfonamide ammonium salt is used), in this step, the organic base used in the previous step remains in the reaction system . Therefore, depending on the amount of the organic base added in the previous step, the amount of the organic base in the present step can be reduced or a required amount of the organic base can be newly added. However, when an amount exceeding the stoichiometric amount with respect to the organic base is used, the reaction rate is increased and the time of the third step can be shortened, but if it is used excessively more than necessary, it is economically disadvantageous. Therefore, the amount of the organic base to be used is preferably 2 to 10 moles, more preferably 2.5 to 5 moles per mole of the perfluoroalkanesulfonamide ammonium salt. If the amount of the organic base is less than 1 mole, the free glass of ammonia may not be sufficiently removed.

The reaction solvent used in this step may be the same as the solvent used in the first step. Further, in the present invention, it is possible to carry out the present step throughout the above-described first to fourth steps, particularly without replacing the solvent.

The same conditions as those described in the first step can be employed for the kind and amount of the solvent when the solvent is added in this step, and the description thereof is not repeated particularly in this step.

The temperature condition is not particularly limited, but it may be performed in a range of -50 to 200 캜. The temperature is usually 0 to 100 占 폚, more preferably 0 to 70 占 폚. When the temperature is lower than -50 占 폚, the reaction rate is lowered, and when the temperature is higher than 200 占 폚, product decomposition may occur.

The pressure conditions are not particularly limited, but may be, for example, in a range of from 0.02 MPa to 3 MPa, preferably from 0.02 MPa to 2 MPa, and more preferably from 0.02 MPa to 1 MPa.

Examples of the reaction vessel used for the reaction include monel, Hastelloy, nickel, or an internal pressure reaction vessel lined with a fluorine resin such as polytetrafluoroethylene or perfluoropolyether resin.

The reaction time is not particularly limited, but may be in the range of 0.1 to 24 hours. Since the reaction time differs depending on the substrate and the reaction conditions, the reaction time can be determined by analyzing means such as gas chromatography, liquid chromatography, ion chromatography, It is preferable to trace the progress of the raw material to the end point at which the raw material is almost lost.

By conducting the first to fourth steps as described above, it is possible to prepare a (fluorosulfonyl) perfluoroalkanesulfonylimide salt by an industrially advantageous production method.

Subsequently, the obtained (fluorosulfonyl) perfluoroalkanesulfonylimide salt is reacted with a hydroxide or carbonate of an alkali metal or a hydroxide or carbonate of an alkaline earth metal to obtain a (fluorosulfonyl) imidazole represented by the formula [3] A method for obtaining a perfluoroalkanesulfonylimidic acid metal salt will be described.

Here, in the formula [3], &quot; M &quot; represents an alkali metal or an alkaline earth metal, which corresponds to alkali metal or alkaline earth metal in a hydroxide or carbonate of an alkali metal or a hydroxide or carbonate of an alkaline earth metal do. In the formula [3], &quot; n &quot; represents an integer equal to the valence of the corresponding metal.

Using as the hydroxides of alkali metals, lithium hydroxide (LiOH), sodium hydroxide (NaOH), potassium hydroxide (KOH), hydroxide, rubidium (RbOH), the cesium hydroxide (CsOH), as the alkali metal carbonate of lithium carbonate (Li ₂ CO ₃ ), sodium carbonate (Na ₂ CO _3), as potassium carbonate (K ₂ CO _3), carbonate, rubidium (Rb ₂ CO _3), cesium carbonate (Cs ₂ CO ₃₎ is, a hydroxide of an alkaline earth metal, magnesium hydroxide (Mg ( OH) _2), calcium hydroxide (Ca (OH) _2), barium hydroxide (Ba (OH) _2), strontium hydroxide (Sr (OH) _2), As the carbonate of an alkaline earth metal carbonate, magnesium carbonate (MgCO _3), calcium carbonate ( (CaCO ₃ ), barium carbonate (BaCO ₃ ), strontium carbonate (SrCO ₃ ), and preferably lithium hydroxide (LiOH), sodium hydroxide (NaOH), potassium hydroxide (KOH), rubidium hydroxide Cesium hydroxide (CsOH), magnesium hydroxide (Mg (OH) ₂ ), calcium hydroxide (Ca (OH) ₂ ), barium hydroxide (Ba (OH) ₂ ) and strontium hydroxide (Sr (OH) ₂ ).

The hydroxides or carbonates of these alkali metals or the hydroxides or carbonates of alkaline earth metals may be used singly or in combination of two or more. When two or more kinds are used, a combination of a hydroxide of the same alkali metal and a carbonate (for example, potassium hydroxide and potassium carbonate) or a combination of a hydroxide of the same alkaline earth metal and a carbonate (for example, magnesium hydroxide and magnesium carbonate) Is preferably used.

The amount of the hydroxide or carbonate of the alkali metal or the hydroxide or carbonate of the alkaline earth metal is preferably 1 to 5 moles per 1 mole of the (fluorosulfonyl) perfluoroalkanesulfonylimide salt, more preferably 1 mole ~ 3 moles. When an amount exceeding 5 moles, that is, an excess amount of a base is allowed to react, the reaction proceeds, but a salt or a complex comprising an imidic acid and an organic base such as the (fluorosulfonyl) perfluoroalkanesulfonylimide salt Is decomposed, and the yield may be lowered. On the other hand, if it is less than 1 mole, the conversion rate may decrease.

When a hydroxide or carbonate of an alkali metal or a hydroxide or carbonate of an alkaline earth metal is reacted, a solvent may be used. For example, when water is used as a solvent, water may be added so that the concentration is usually 10% by mass to 70% by mass, preferably 20% by mass to 60% by mass, and more preferably 30% by mass to 60% by mass. When the amount of water is too small, stirring in the reaction system becomes difficult, and in a case where the amount is excessively large, a case where the post-reaction treatment becomes complicated or a reaction vessel which is larger than usual is required.

An organic solvent other than water may also be used. And ethers such as diethyl ether, dioxane, tetrahydrofuran and ethylene glycol dimethyl ether. It may also be used in combination with water. The amount of the solvent to be used is appropriately selected in the range of usually 0.5 to 10 times, preferably 1 to 7 times, the (fluorosulfonyl) perfluoroalkanesulfonylimide salt. However, since the reaction proceeds sufficiently even with the use of water, the merit of using an organic solvent other than water is small.

The reaction temperature is not particularly limited, but is usually -10 ° C to 110 ° C, preferably 25 to 80 ° C. If the reaction temperature is lower than -10 ° C, the reaction does not proceed sufficiently, leading to a reduction in the yield, resulting in economical disadvantage, or a decrease in the reaction rate, requiring a long time until the completion of the reaction. On the other hand, if it exceeds 110 ° C, by-products tend to be generated, and excessive heating results in poor energy efficiency.

The reaction time is not particularly limited, but usually it is within a range of 24 hours, and the progress of the reaction is tracked by analyzing means such as ion chromatography, NMR, etc., and the point where the raw material substrate is almost lost is set as the end point .

The reactor used in the present step may be a metal container such as stainless steel, Hastelloy or Monel, or a metal container made of a tetrafluoroethylene resin, a chlorotrifluoroethylene resin, a vinylidene fluoride resin, a PFA resin, a polypropylene resin, a polyethylene resin, Or the like, or a reactor capable of sufficiently carrying out the reaction under atmospheric pressure or under pressure can be used.

[Example]

Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited to these embodiments.

Example 1

Step 1:

300 g of acetonitrile was charged into a 500-ml stainless steel autoclave reactor, and the reactor was cooled. When the temperature reached 5 ° C or less, the reactor was degassed.

After degassing, 24.7 g (1.45 mol) of anhydrous ammonia was added, and then 66.3 g (0.436 mol) of trifluoromethanesulfonyl fluoride was added slowly while maintaining the internal temperature at 0 to 5 ° C. When introduction of trifluoromethanesulfonyl fluoride was completed, stirring was continued for 13 hours. After 13 hours, the reaction solution was quantified by ¹⁹ F NMR, and as a result, 0.415 mol (yield: 95.1%) of trifluoromethanesulfonamide ammonium salt was obtained.

Step 2:

The reaction solution obtained in the first step was heated to 40 占 폚, and filtration under reduced pressure was carried out using a kiriyama lot. After filtration, the content of ammonium fluoride in the filtrate was confirmed by ion chromatography to be 0.0046 mol, confirming that 99% of the filtrate could be removed.

Step 3:

The solution obtained in the second step was transferred to a reactor equipped with a dimroth cooling tube, and 126 g (1.25 mol) of triethylamine was added and heated at 50 to 55 占 폚 under reduced pressure of 0.064 to 0.068 MPa for 12 hours, Ammonia was released. After the reaction, the content of ammonium ion was confirmed by ion chromatography, and it was confirmed that the content was reduced from 0.42 mol to 0.0007 mol (reduction rate: 99.8%).

Step 4:

The solution obtained in the third step was placed in a 1000 ml stainless steel autoclave reactor, and the reactor was cooled. When the temperature reached 5 ° C or lower, the reactor was degassed. After degassing, 63.15 g (0.623 mol) of sulfuryl fluoride was slowly added while maintaining the internal temperature at 0-5 &lt; 0 &gt; C. When the introduction of sulfuryl fluoride was completed, stirring was continued for 17 hours. After 17 hours, the reaction solution was quantified by ¹⁹ F NMR to obtain 0.404 mol of triethylammonium (fluorosulfonyl) trifluoromethanesulfonylimide salt as a target at a yield of 92.3%.

Example 2

Step 1:

300 g of acetonitrile was charged into a 500-ml stainless steel autoclave reactor, and the reactor was cooled. When the temperature reached 5 ° C or less, the reactor was degassed. After degassing, 24.7 g (1.45 mol) of anhydrous ammonia was added, and 88.1 g (0.436 mol) of pentafluoroethanesulfonyl fluoride was slowly added thereto while maintaining the internal temperature at 0 to 5 ° C. When introduction of pentafluoroethanesulfonyl fluoride was completed, stirring was continued for 69 hours. After 69 hours, the reaction solution was quantified by ¹⁹ F NMR, and as a result, 0.369 mol (yield: 84.7%) of ammonium trifluoromethanesulfonamide was obtained.

Step 2 to Step 4:

After the second step, the reaction was carried out in the same manner as in Example 1. As a result, 0.337 mol of triethylammonium (fluorosulfonyl) pentafluoroethanesulfonylimide salt as a target product was obtained in a yield of 77.3%.

Example 3

Step 1:

200 g of acetonitrile was placed in a 500-ml stainless steel autoclave reactor, the reactor was cooled, and the reactor was degassed when the temperature reached 5 ° C or lower. After the degassing, 12.3 g (0.725 mol) of anhydrous ammonia was added, and then 65.9 g (0.218 mol) of nonafluorobutane sulfonyl fluoride was added slowly while maintaining the internal temperature at 0 to 5 ° C. After the introduction of nonafluorobutane sulfonyl fluoride was completed, stirring was continued for 22 hours. After 22 hours, the reaction solution was quantified by ¹⁹ F NMR, and as a result, 0.177 mol (yield: 81.2%) of nonafluorobutane sulfonamide ammonium salt was obtained.

Step 2 to Step 4:

After the second step, the reaction was carried out in the same manner as in Example 1. As a result, a target triethylammonium (fluorosulfonyl) nonafluorobutanesulfonylimide salt was obtained in an amount of 0.157 mol (yield: 72.3%).

Example 4

Step 1:

300 g of acetonitrile was charged into a 500-ml stainless steel autoclave reactor, and the reactor was cooled. When the temperature reached 5 ° C or less, the reactor was degassed. After degassing, 24.7 g (1.45 mol) of anhydrous ammonia was added, and then 66.3 g (0.436 mol) of trifluoromethanesulfonyl fluoride was added slowly while maintaining the internal temperature at 0 to 5 ° C. When the introduction of trifluoromethanesulfonyl fluoride was completed, stirring was continued for 18 hours. After 18 hours, the reaction solution was quantified by ¹⁹ F NMR, and as a result, 0.415 mol (yield: 95.1%) of ammonium trifluoromethanesulfonamide salt was obtained.

Step 2:

The reaction solution obtained in the first step was filtrated under reduced pressure using Kiriyama lot at room temperature to obtain 400 g of a filtrate. ^As a result of quantitative analysis by ¹⁹ F NMR, it was confirmed that 0.415 mol of the trifluoromethanesulfonamide ammonium salt was contained in the filtered filtrate. Further, the content of ammonium fluoride in the filtrated filtrate was confirmed by ion chromatography to be 0.0112 mol, and it was confirmed that it was possible to remove 97%.

Step 3 to Step 4:

After the third step, the reaction was carried out in the same manner as in Example 1, except that 91.4 g (1.25 mol) of diethylamine was used instead of triethylamine, thereby obtaining the target diethylammonium (fluorosulfonyl) trifluoro To obtain 0.376 mol of lomesulfonylimide salt in a yield of 86.2%.

Example 5

Step 1:

300 g of acetonitrile was charged into a 500-ml stainless steel autoclave reactor, and the reactor was cooled. When the temperature reached 5 ° C or less, the reactor was degassed. After degassing, 24.7 g (1.45 mol) of anhydrous ammonia was added, and then 66.3 g (0.436 mol) of trifluoromethanesulfonyl fluoride was added slowly while maintaining the internal temperature at 0 to 5 ° C. When the introduction of trifluoromethanesulfonyl fluoride was completed, stirring was continued for 15 hours. After 15 hours, the reaction solution was quantified by ¹⁹ F NMR, and 0.415 mol (yield: 95.1%) of ammonium trifluoromethanesulfonamide salt was obtained.

Step 2:

The reaction solution obtained in the first step was subjected to filtration under reduced pressure at room temperature under Kiriyama lot, and 400 g of a filtrate was obtained. ^As a result of quantitative analysis by ¹⁹ F NMR, it was confirmed that 0.415 mol of the trifluoromethanesulfonamide ammonium salt was contained in the filtered filtrate. Further, the content of ammonium fluoride in the filtrated filtrate was confirmed by ion chromatography to be 0.0112 mol, and it was confirmed that it was possible to remove 97%.

Step 3 to Step 4:

After the third step, the reaction was carried out in the same manner as in Example 1, except that 98.8 g (1.25 mol) of pyridine was used instead of triethylamine to obtain the desired pyridinium- (fluorosulfonyl) trifluoro Methanesulfonylimide salt (0.358 mol) in a yield of 82.1%.

[Comparative Example 1]

Step 1:

300 g of acetonitrile was charged into a 500-ml stainless steel autoclave reactor, and the reactor was cooled. When the temperature reached 5 ° C or less, the reactor was degassed. After degassing, 24.7 g (1.45 mol) of anhydrous ammonia was added, and then 66.3 g (0.436 mol) of trifluoromethanesulfonyl fluoride was added slowly while maintaining the internal temperature at 0 to 5 ° C. When the introduction of trifluoromethanesulfonyl fluoride was completed, stirring was continued for 15 hours. After 15 hours, the reaction solution was quantified by ¹⁹ F NMR, and 0.415 mol (yield: 95.1%) of ammonium trifluoromethanesulfonamide salt was obtained.

Subsequently, the reaction was carried out in the same manner as in the third and fourth steps of Example 1, except that 162 g (1.60 mol) of triethylamine was added to the solution obtained in the first step, thereby obtaining triethyl 0.264 mol of ammonium (fluorosulfonyl) trifluoromethanesulfonylimide salt was obtained in a yield of 60.6%.

That is, when the third step and the fourth step are carried out without carrying out the second step, the yield of the (fluorosulfonyl) perfluoroalkanesulfonylimide salt is remarkably lowered. This is presumed that a large amount of ammonium cation is present in the reaction system, and side reactions are likely to occur.

Example 6

Then, an aqueous solution containing 0.404 mol (134.2 g) of triethylammonium (fluorosulfonyl) trifluoromethanesulfonylimide salt obtained in Example 1 and 24.9 g of potassium hydroxide was mixed at room temperature and stirred for 1 hour did. After stirring, triethylamine and water contained in the reaction mixture were distilled off to obtain (fluorosulfonyl) trifluoromethanesulfonylimide potassium. Acetonitrile was added thereto to separate the un-dissolved components, and acetonitrile was distilled off to obtain 87.0 g of (fluorosulfonyl) trifluoromethanesulfonylimide potassium having a purity of 99% or more at a yield of 80%.

Example 7

Subsequently, except that an aqueous solution containing 0.337 mol (128.8 g) of triethylammonium (fluorosulfonyl) pentafluoroethanesulfonylimide salt obtained in Example 2 and 8.9 g of lithium hydroxide was mixed at room temperature, The same operation as in Example 6 was carried out. As a result, 75.5 g of (fluorosulfonyl) pentafluoromethanesulfonylimide lithium having a purity of 99% was obtained in a yield of 78%.

The (fluorosulfonyl) perfluoroalkanesulfonylimide salt of the present invention can be used as medicines, intermediates for pesticides, cell electrolytes, and acid catalysts.

Claims (11)

Equation [1]:
[Chemical formula 10]

_Wherein R _f represents a linear or branched perfluoroalkyl group having 1 to 6 carbon atoms and B represents an organic base,
A process for producing a (fluorosulfonyl) perfluoroalkanesulfonylimide salt represented by the general formula (1), comprising the following steps:
[First Step]
Equation [2]:
(11)

_Wherein R _f represents a linear or branched perfluoroalkyl group having 1 to 6 carbon atoms and X represents a halogen atom,
(NH ₃ ) in the presence of a solvent to obtain a solution containing an ammonium salt of perfluoroalkanesulfonamide and an ammonium halide, by reacting perfluoroalkanesulfonyl halide represented by the general formula
[Second Step]
A step of separating and removing the ammonium halide contained in the solution by filtering (separately) the solution obtained in the first step to obtain a solution containing an ammonium perfluoroalkanesulfonamide salt.
[Third Step]
To the solution containing the perfluoroalkanesulfonamide ammonium salt obtained in the second step, an organic base was added to obtain a solution containing the &quot; salt of perfluoroalkanesulfonamide and organic base &quot; and ammonia, Ammonia is separated and removed from the solution, and the organic base is used in an amount of 2 to 10 moles per mole of the perfluoroalkanesulfonamide ammonium salt.
[Fourth Step]
(Fluorosulfonyl) purple in the presence of an organic base with respect to a solution containing &quot; a salt of a perfluoroalkanesulfonamide and a salt of an organic base &quot; obtained by separating and removing ammonia in a third step A process for obtaining a fluoroalkanesulfonylimide salt. The method according to claim 1,
In the first step, the solvent is acetonitrile, propionitrile, dimethylsulfoxide, sultone, diglyme, tetrahydrofuran or dimethylformamide. The method according to claim 1,
Wherein the reaction temperature is 0 ° C to 100 ° C in the first step. 3. The method of claim 2,
Wherein the reaction temperature is 0 ° C to 100 ° C in the first step. The method according to claim 1,
And the temperature at the time of separation is 10 占 폚 to 80 占 폚 in the second step. The method according to claim 1,
In the third step, when separating and removing ammonia from the solution containing a solution containing "perfluoroalkanesulfonamide and a salt of an organic base" and ammonia under a pressure of 0.02 MPa to 0.1 MPa at 20 ° C To &lt; RTI ID = 0.0 &gt; 80 C. &lt; / RTI &gt; The method according to claim 1,
In the first step, the amount of ammonia to be used is 3 to 10 moles per mole of the perfluoroalkanesulfonyl halide. The method according to claim 1,
In the third step and the fourth step, the amount of the organic base to be used is 2 to 10 moles per mole of the perfluoroalkanesulfonamide ammonium salt. The method according to claim 1,
In the fourth step, the amount of the sulfuryl fluoride to be used is 1 mole to 10 moles per mole of the perfluoroalkanesulfonamide and the salt of the organic base. A process for producing a (fluorosulfonyl) perfluoroalkanesulfonylimide salt by the method according to any one of claims 1 to 9, followed by reacting the (fluorosulfonyl) perfluoroalkanesulfonylimide salt Is reacted with a hydroxide or carbonate of an alkali metal or a hydroxide or carbonate of an alkaline earth metal.
[Chemical Formula 12]

[In the formula [3], R _f is the same as the formula [1] of the first claim. M represents an alkali metal or an alkaline earth metal. and n represents an integer equal to the valence of the corresponding metal.]
(Fluorosulfonyl) perfluoroalkanesulfonylimidic acid metal salt represented by the formula (I). 11. The method of claim 10,
Wherein the amount of the hydroxide or carbonate of the alkali metal or the hydroxide or carbonate of the alkaline earth metal is 1 to 5 moles per mole of the (fluorosulfonyl) perfluoroalkanesulfonylimide salt.