JP5461401B2 - Method for producing bis (fluorosulfonyl) imide anion compound - Google Patents

Description

  The present invention relates to a method for producing a bis (fluorosulfonyl) imide anion compound used for the synthesis of battery electrolytes and ionic liquids and the like, and an ion-pair compound containing a bis (fluorosulfonyl) imide anion compound obtained by the production method. is there.

  Many anionic compounds containing elemental fluorine have been reported and are useful, but most of the synthesis methods require special equipment such as electrolytic fluorine. The production method of the bis (fluorosulfonyl) imide anion, which is an anion containing fluorine element, is disclosed as a method using a very expensive raw material such as fluorosulfonic acid or fluoroisocyanate, or a reaction with a low yield. In many cases, it is a method that uses. Alternatively, a gas that is not easy to handle is used, which is not preferable in terms of cost for production by a general industrial technique.

  For example, Japanese Patent Laid-Open No. 8-511274 discloses a reaction between fluorosulfonic acid and urea, but uses a strongly acidic raw material and is very difficult to handle.

  In addition, a method of synthesizing a bis (chlorosulfonyl) imide compound and converting a chlorine atom to a fluorine atom is disclosed, but high-cost chlorosulfonyl isocyanate is used as a raw material, and residual halogen is contained as an impurity. There are problems such as being.

  In Japanese translations of PCT publication No. 2004-522681, an example of fluorination under mild conditions of 80 ° C. or lower is reported. However, an expensive solvent such as nitromethane is substantially used, and the fluoride salt used is NaF or KF. In this case, since 8 equivalents are used, it is not industrially advantageous. In addition, it takes 30 hours or more to convert 98% of the starting material.

Martin et al. (Z. Anorg. Allg. Chem. 631, 55 (2005)) discloses a synthesis method using raw materials composed of urea and fluorosulfonic acid, but impurities such as fluorosulfonic acid remain. There is a problem. Moreover, although the synthesis method which consists of sulfamic acid, thionyl chloride, and fluorosulfonic acid is also disclosed, many mixtures of a fluoride and a chloride exist. Furthermore, a reaction using chlorosulfonic acid instead of fluorosulfonic acid, which is difficult to use industrially, is disclosed, but the reaction takes 24 hours or more, and a reaction bath is also used in the fluorination reaction. It is necessary to set the temperature to 120 ° C. and further to 170 ° C. to 180 ° C., and the purity of the product cannot be said to be sufficient due to the side reaction, and it is assumed that the yield is low because it includes many steps for purification. .
JP-A-8-511274 JP-T-2004-522681 Z. Anorg. Allg. Chem. 631, 55 (2005)

  Thus, in order to synthesize a bis (fluorosulfonyl) imide anion compound, it is necessary to use a high cost and low yield reaction in the conventional production method, and the obtained bis (fluorosulfonyl) imide compound The purity of was not high.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have carried out fluorine substitution on a bis (chlorosulfonyl) imide compound obtained using sulfamic acid, chlorosulfonic acid and a halogenating agent as raw materials. Thus, it was found that the bis (fluorosulfonyl) imide anion compound can be obtained in sufficient yield and high purity, and the production method of the bis (fluorosulfonyl) imide anion compound of the present invention has been completed.

  According to the present invention, the reaction is controlled, and by using a basic catalyst together with an alkali metal fluoride salt in a halogen exchange fluorination reaction, efficient fluorination is possible, and there is almost no residual halogen atom other than fluorine. A pure bis (fluorosulfonyl) imide anion compound can be obtained with sufficient yield and cost.

  The sulfamic acid used in the present invention is not particularly limited, but preferably subjected to a drying treatment. Although it does not specifically limit as a drying process, Heat drying, reduced pressure drying, and the storage in a dry gas can be mentioned.

  In heat drying, sulfamic acid can be dried by heating at 60 ° C. or higher, preferably 80 ° C. or higher. In vacuum drying, the pressure is preferably 10 kPa · s or less, and drying is accelerated by heating. It can also be dried by leaving it in a dry gas environment such as dry air, nitrogen, argon or helium for a long time. These drying methods may be used alone or in combination with, for example, introducing a dry gas into heat drying and vacuum drying.

  The container used for these drying is not specifically limited, You may introduce into a reaction container what was dried with the dryer. Alternatively, sulfamic acid may be introduced into the reaction vessel in advance, and one or more of heating, decompression and introduction of dry gas may be appropriately performed.

  The moisture content of the dried sulfamic acid is preferably 1% (% by weight, hereinafter the same) or less, and more preferably 0.1% or less.

  The chlorosulfonic acid used in the present invention is not particularly limited, but is preferably stored in a state where moisture is blocked and preferably has a purity of 95% or more, more preferably 98% or more. The thing stored in the state in which the water | moisture content mixes brings about a purity fall, and when the purity is less than 95%, it will bring about the fall of a yield.

  Although the halogenating agent used in the present invention is not particularly limited, phosphorus trichloride, phosphorus pentachloride and thionyl chloride are preferable from the viewpoint of easy handling, and thionyl chloride is particularly preferable from the viewpoint of easy removal of by-products.

  Similarly, the halogenating agent is stored in a state where moisture is blocked, and preferably has a purity of 95% or more, more preferably 98% or more.

  The blending amount of sulfamic acid, chlorosulfonic acid, and halogenating agent is preferably 0.9 to 1.1 mol of chlorosulfonic acid with respect to 1 mol of sulfamic acid. Furthermore, it is particularly preferable to add 0.95 to 1.05 mol of chlorosulfonic acid. If the chlorosulfonic acid is less than 0.9 mol, the unreacted intermediate remains and the purity and yield are low. If the chlorosulfonic acid exceeds 1.1 mol, the chlorosulfonic acid remains and it is necessary to remove the strongly acidic substance. .

  The halogenating agent is preferably added in an amount of 2.0 to 4.0 mol, more preferably 2.2 to 3.0 mol, per 1 mol of sulfamic acid. When the halogenating agent is less than 2.0 mol, the yield and purity are lowered. If the halogenating agent exceeds 4.0 mol, the cost increases.

  The order of introducing the sulfamic acid, chlorosulfonic acid, and halogenating agent into the reactor is not particularly limited, but it is preferable to introduce them at 80 ° C. or lower. When introduced at a temperature exceeding 80 ° C., the volatilization of the raw material causes coloring, a decrease in yield, and a decrease in purity. Furthermore, it is more preferable to introduce at 60 ° C. or less from the viewpoint of safety.

  When introducing the raw material, it is preferable to prevent moisture from entering, and it is preferable to replace the reaction vessel with a dry gas. The dry gas used at the time of introduction is not particularly limited, but the moisture is preferably 1% or less, and more preferably 0.1% or less. Examples of the dry gas include dry air, nitrogen, argon, helium, carbon dioxide, and the like. Among these, a gas containing no oxygen is preferable for the fluorine substitution reaction to be performed continuously.

  The introduced sulfamic acid, chlorosulfonic acid, and halogenating agent are mixed with stirring, and the reaction is carried out by heating. The reaction is heated from the introduction temperature of the raw material to the reaction reaching temperature as needed. The method for heating the reaction vessel is not particularly limited, and examples include heating with steam, heating with a heat medium, and heating with an electric heater. The contents are preferably heated with boiling and reflux conditions appropriately controlled. The time required for the temperature rise is preferably 24 hours or less, and more preferably 12 hours or less. When the time required for temperature rise exceeds 24 hours, the yield decreases.

  In the reaction, the solution temperature is preferably reached at 100 to 150 ° C, more preferably at 105 to 140 ° C, and most preferably at 110 to 130 ° C. When the solution temperature is less than 100 ° C., the reaction is not completed, and the yield and purity tend to decrease. When the solution temperature exceeds 150 ° C., it is colored due to thermal decomposition of the introduced raw materials and reaction products, resulting in a decrease in purity and yield.

  The reaction time is preferably maintained within 24 hours after reaching the reaction temperature, and the reaction time is more preferably within 12 hours, most preferably within 6 hours from the viewpoint of time reduction and cost reduction. preferable. If it exceeds 24 hours, the coloring becomes strong, and the purity and yield decrease.

  Further, during the reaction, it is preferable to introduce a dry gas into the reaction solution and the space above the reaction solution. The dry gas used during the reaction is preferably a gas that does not contain oxygen, such as nitrogen, argon, helium, and carbon dioxide, preferably has a moisture content of 0.5% or less, and more preferably has a moisture content of 0.1% or less. The oxygen concentration is preferably 1% or less. When the moisture content of the dry gas exceeds 0.1%, the yield and purity are lowered, and when the oxygen concentration exceeds 1%, coloring occurs and the purity is lowered. The amount of the dry gas introduced is preferably 0.005 to 10 liter / min with respect to 1 mol of sulfamic acid.

  By-products such as hydrochloric acid and sulfur dioxide are preferably removed by gas, and are preferably removed from the reaction vessel by the introduced dry gas stream from the viewpoint of yield and purity. Therefore, the most preferred dry gas is nitrogen, argon or helium.

  In this reaction, there is no need for a catalyst, but it can also be added.

  As the catalyst that can be added, a base catalyst is preferable, and aliphatic tertiary amine compounds such as trimethylamine, triethylamine, tripropylamine, tributylamine, tri (hydroxyethyl) amine, methylpiperidine, dimethylpiperazine, diazabicyclooctane, Trialkylphosphine such as trimethylphosphine and triethylphosphine is preferable. The catalyst is preferably added in the range of 0.0001 to 0.1 mol with respect to 1 mol of sulfamic acid.

  In this reaction, a solvent is not necessary, but can be added. Although it does not specifically limit as a solvent which can be added, The compound which does not have an aromatic proton is preferable.

  The bis (chlorosulfonyl) imidic acid obtained by this reaction may be subjected to fluorine substitution as it is, or may be once transferred to a storage container for storage. Furthermore, fluorine substitution may be performed as a bis (chlorosulfonyl) imidoate by a neutralization reaction, and it may be once stored in a storage container.

  Compounds used for neutralization include hydroxides and carbonates of alkali metals such as potassium, sodium, lithium, and calcium. To prevent water generated from the neutralization reaction, potassium chloride, sodium chloride, lithium chloride, It is preferable to carry out dehydrohalogenation using halides such as calcium chloride, potassium bromide and potassium iodide.

  Bis (chlorosulfonyl) imidic acid or bis (chlorosulfonyl) imidate can be converted to a bis (fluorosulfonyl) imide salt compound by fluorine substitution.

The fluoride salt used for the fluorine substitution is not particularly limited, but ion pair compounds having a fluorine atom such as hydrofluoric acid, ammonium fluoride, metal fluoride, and quaternary ammonium fluoride salt can be exemplified. From this point, metal fluoride is preferable, and LiF, KF, CaF ₂ , CsF, and RbF are more preferable because of reactivity. These fluoride salts are preferably dried well, preferably have a moisture content of 0.5% or less, more preferably 0.2% or less, and 0.1% or less. Is most preferred. If the water content exceeds 0.5%, the reaction rate of the fluorine substitution decreases, and an excessive fluoride salt is required, resulting in an increase in cost.

  The method for drying the fluoride salt is not particularly limited, and heat drying, hot air drying, reduced pressure drying, drying with a dry gas, and the like can be used. Furthermore, you may dry directly by pressure reduction or superheating in the reaction container used for fluorine substitution. Or after dispersing in an organic solvent to form a slurry, drying may be performed by mixing a dehydrating agent such as molecular sieve.

  The shape of the fluoride salt used in this reaction is not particularly limited, but those having a large surface area are preferred. Examples of the method for increasing the surface area include a spray drying method and a mechanical pulverization method using a bead mill or a ball mill. Of these, those spray-dried are particularly preferred.

  These fluoride salts can be used alone or in combination of a plurality of fluoride salts. Although the amount of these fluoride salts is not particularly limited, it is preferably used in an amount of 3.0 to 9.0 mol with respect to 1 mol of bis (chlorosulfonyl) imidic acid. Furthermore, it is preferable to use at 3.0-5.0 mol from the point of cost. It is preferably used in an amount of 2.0 to 6.0 mol with respect to 1 mol of bis (chlorosulfonyl) imidate, and particularly preferably 2.0 to 3.0 mol in terms of cost.

  Fluorine substitution is carried out by mixing bis (chlorosulfonyl) imidic acid or bis (chlorosulfonyl) imidate with a fluoride salt. The mixing method is not particularly limited, and examples thereof include direct mixing with a fluoride salt, mixing into a slurry in which the fluoride salt is dispersed, introduction into a column packed with fluoride salt, and the like.

  In fluorine substitution, a catalyst may be added. The catalyst that can be added is not particularly limited, but a base catalyst is particularly preferable. Base catalysts include primary amines such as ammonia, methylamine, ethylamine, propylamine, hydroxyethylamine, aniline, dimethylamine, methylethylamine, diethylamine, dipropylamine, dibutylamine, dihydroxyethylamine, piperidine, piperazine, and diphenylamine. Tertiary amine, trimethylamine, diethylmethylamine, ethyldimethylamine, triethylamine, tripropylamine, tributylamine, tri (hydroxyethyl) amine, tertiary amines such as methylpiperidine, dimethylpiperazine, aromatics such as pyridine, imidazole, methylimidazole Examples are amines, and these salts are also included. Furthermore, a tertiary amine and an aromatic amine are preferable from the viewpoint of reactivity and the like, and triethylamine and pyridine are particularly preferable from the viewpoint of cost and ease of removal.

  These base catalysts can be used alone or in combination of a plurality of base catalysts.

  The base catalyst can be used regardless of the presence or absence of a reaction solvent, and in the range of 0.0001 to 1.2 mol per 1 mol of bis (chlorosulfonyl) imidic acid or bis (chlorosulfonyl) imidate from the viewpoint of cost. It is preferable to add at.

  The fluorine substitution can be carried out without a solvent or by adding a solvent.

  Solvents that can be added are not particularly limited, but aromatic solvents such as benzene, toluene, xylene, and anisole, ester solvents such as ethyl acetate, propyl acetate, and butyl acetate, ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, methyl Ether solvents such as ethyl ether, diethyl ether, tetrahydrofuran and dioxane, alcohol solvents such as methanol, ethanol, propanol and butanol, aprotic polarities such as acetonitrile, nitromethane, dimethyl sulfoxide, N, N-dimethylformamide and benzonitrile A solvent etc. are illustrated. Furthermore, aprotic polar solvents, ester solvents, and ether solvents are preferable from the viewpoint of reaction rate and yield, and acetonitrile, N, N-dimethylformamide, tetrahydrofuran, dioxane, and ethyl acetate are particularly preferable from the viewpoint of cost and solvent removal. .

  These solvents can be used alone or as a mixture of a plurality of solvents.

  In fluorine substitution, the reaction temperature is not particularly limited, but it is preferably controlled in the range of 5 to 100 ° C, more preferably in the range of 5 to 70 ° C. When the reaction temperature is less than 5 ° C., the reaction rate becomes slow and a reaction time is required. When reaction temperature exceeds 100 degreeC, coloring will become large and purity and a yield will fall.

  In addition, it is preferable to prevent moisture from being mixed in the fluorine substitution. Although it does not specifically limit as a method of preventing mixing of water | moisture content, The method of implementing reaction in a sealed state or introduce | transducing dry gas into a reaction container can be used. Examples of the dry gas that can be used include dry air, nitrogen, argon, helium, carbon dioxide, and the like. The moisture is preferably 0.5% or less, and more preferably 0.1% or less. . If the moisture content of the dry gas exceeds 0.5%, the yield and purity are lowered.

  The bis (fluorosulfonyl) imido acid salt obtained by the reaction can be used as it is. Further, the purity may be further increased by purification.

  Although it does not specifically limit as a purification method, Reprecipitation using a solvent or recrystallization, distillation of bis (fluorosulfonyl) imido acid, etc. can be illustrated.

  Examples will be described below, but the present invention is not limited to these examples.

[ Reference Example 1 ]
30 g (0.31 mol) of sulfamic acid (manufactured by Wako Pure Chemical Industries, Ltd., purity 99.5% or more) was dried with a heat dryer at 50 ° C. for 1 hour, and the water content after drying was 1500 ppm. A 300 ml flask equipped with a reflux condenser, a thermometer, a stirrer, a heating device, and a dry gas introduction tube was dried by heating and cooled to room temperature, and then 30 g (0.31 mol) of dried sulfamic acid and chlorosulfonic acid (sum) 38 g (0.33 mol) with a purity of 97% or more manufactured by Kojun Pharmaceutical Co., Ltd., and 106 g (0.77 mol) of phosphorus trichloride (99% or more with a purity of Wako Pure Chemical Industries) were slowly added dropwise, and dry nitrogen (dew point -60 C. or less) was introduced at 0.02 liter / min for 60 minutes. The vessel was then heated to 110 ° C. over 4 hours and maintained at the reaction temperature for 10 hours, and then cooled to room temperature, yielding 90 g of reactant A-1 containing bis (chlorosulfonyl) imidic acid.

Next, 90 g (1.55 mol) of potassium fluoride (spray-dried product manufactured by Wako Pure Chemical Industries, Ltd.) whose water content became 200 ppm or less by drying at 60 ° C. and 1.3 kPa for 3 hours and water by drying with molecular sieve 1000 g of acetonitrile (purity 99% or more manufactured by Wako Pure Chemical Industries, Ltd.) with a water content of 100 ppm or less, and 6 g (0.06 mol) of triethylamine (purity 98% or more manufactured by Wako Pure Chemical Industries, Ltd.) dried with molecular sieves and having a water content of 500 ppm or less. The flask was placed in a 2 liter flask, a reflux condenser, a thermometer, a stirrer, and a heating device were set, and dry nitrogen (dew point: −60 ° C. or lower) was introduced at 0.05 liter / min. Next, 90 g of the reactant A-1 was dropped over 2 hours while cooling the solution, and then kept at a temperature of 25 ° C. for 48 hours. Thereafter, the reaction solution was filtered and concentrated, and further dissolved in ethanol at 60 ° C. and cooled to obtain 35 g of white crystals. The resulting white crystals infrared spectroscopy results ^{845cm -1, 1188cm -1,} identified from the absorption spectrum, etc. 1382Cm ^-1 bis and (fluorosulfonyl) imide potassium, inductively coupled plasma emission spectrometry results, the impurity chlorine Was 2.5 ppm, and the yield was 52%.

[ Reference Example 2 ]
30 g (0.31 mol) of sulfamic acid (manufactured by Wako Pure Chemical Industries, Ltd., purity 99.5% or more) was dried at room temperature under a reduced pressure of 1.6 kPa for 8 hours, and the water content after drying was 600 ppm. A 300 ml flask equipped with a reflux condenser, a thermometer, a stirrer, a heating device, and a dry gas introduction tube was dried by heating and cooled to room temperature, and then 30 g (0.31 mol) of dried sulfamic acid and chlorosulfonic acid (sum) 38 g (0.33 mol) with a purity of 97% or more manufactured by Koyo Pure Chemical Co., Ltd., and 130 g (0.61 mol) of phosphorus pentachloride (99% or more of purity manufactured by Wako Pure Chemical Industries, Ltd.) are slowly added dropwise to dry nitrogen (dew point -60 C. or less) was introduced at 0.02 liter / min for 60 minutes. Next, the temperature of the vessel was raised to 110 ° C. over 4 hours, and after maintaining this reaction temperature for 16 hours, the vessel was cooled to room temperature to obtain 115 g of reactant A-2 containing bis (chlorosulfonyl) imidic acid.

Next, 90 g (1.55 mol) of potassium fluoride (spray-dried product manufactured by Wako Pure Chemical Industries, Ltd.) whose water content was reduced to 200 ppm or less by drying at 1.3 kPa at 60 ° C. for 3 hours and water was dried by molecular sieve. 1100 g of dioxane (purity 99% or more manufactured by Wako Pure Chemical Industries, Ltd.) with a water content of 100 ppm or less, 8 g (0.08 mol) of triethylamine (purity 98% or more manufactured by Wako Pure Chemical Industries, Ltd.) dried with molecular sieves and having a water content of 500 ppm or less. The flask was placed in a 2 liter flask, a reflux condenser, a thermometer, a stirrer, and a heating device were set, and dry nitrogen (dew point: −60 ° C. or lower) was introduced at 0.05 liter / min. Next, 115 g of reactant A-2 was added dropwise over 2 hours while cooling the solution, and then maintained at a temperature of 25 ° C. for 48 hours. Thereafter, the reaction solution was filtered and concentrated, further dissolved in ethanol at 60 ° C., and cooled to obtain 40 g of white crystals. The resulting white crystals infrared spectroscopy results ^{845cm -1, 1188cm -1,} identified from the absorption spectrum, etc. 1382Cm ^-1 bis and (fluorosulfonyl) imide potassium, inductively coupled plasma emission spectrometry results, the impurity chlorine Was 15.2 ppm and the yield was 59%.

[Example 1 ]
30 g (0.31 mol) of sulfamic acid (manufactured by Wako Pure Chemical Industries, Ltd., purity 99.5% or more) was dried with a heat dryer at 50 ° C. for 1 hour, and the water content after drying was 1500 ppm. A 300 ml flask equipped with a reflux condenser, a thermometer, a stirrer, a heating device, and a dry gas introduction tube was dried by heating and cooled to room temperature, and then 30 g (0.31 mol) of dried sulfamic acid and chlorosulfonic acid (sum) 35 g (0.30 mol) with a purity of 97% or more, manufactured by Kojun Pharmaceutical Co., Ltd., 146 g (1.08 mol) of thionyl chloride (95% or more of purity manufactured by Wako Pure Chemical Industries) were added, and dry nitrogen (dew point -60 ° C or less) Was introduced at 0.02 liter / min for 60 minutes. The vessel was then heated to 130 ° C. over 8 hours and maintained at the reaction temperature for 4 hours, and then cooled to room temperature, yielding 65 g of reactant A-3 containing bis (chlorosulfonyl) imidic acid.

Next, 65 g (1.12 mol) of potassium fluoride (spray-dried product manufactured by Wako Pure Chemical Industries, Ltd.) whose water content was reduced to 200 ppm or less by drying at 60 ° C. and 1.3 kPa for 3 hours, and water by drying with molecular sieves. 1000 g of acetonitrile (purity 99% or more manufactured by Wako Pure Chemical Industries, Ltd.) with a water content of 300 ppm or less, and 2 g (0.02 mol) of triethylamine (purity 98% or more manufactured by Wako Pure Chemical Industries, Ltd.) dried with molecular sieves and having a water content of 500 ppm or less. The flask was placed in a 2 liter flask, a reflux condenser, a thermometer, a stirrer, and a heating device were set, and dry nitrogen (dew point: −60 ° C. or lower) was introduced at 0.05 liter / min. Next, 65 g of the reaction product A-3 was dropped over 2 hours while cooling the solution, and then kept at a temperature of 40 ° C. for 8 hours. Thereafter, the reaction solution was filtered and concentrated to obtain 62 g of white crystals. The resulting white crystals result of infrared spectrum ^{analysis, 845cm -1, 1188cm -1,} identified from the absorption spectrum, etc. 1382Cm ^-1 bis and (fluorosulfonyl) imide potassium, inductively coupled plasma emission spectrometry results, the impurity Chlorine was 1.5 ppm and the yield was 92%.

[ Reference Example 3 ]
30 g (0.31 mol) of sulfamic acid (manufactured by Wako Pure Chemical Industries, Ltd., purity 99.5% or more) was dried with a heat dryer at 50 ° C. for 1 hour, and the water content after drying was 1500 ppm. A 300 ml flask equipped with a reflux condenser, a thermometer, a stirrer, a heating device, and a dry gas introduction tube was dried by heating and cooled to room temperature, and then 30 g (0.31 mol) of dried sulfamic acid and chlorosulfonic acid (sum) 36 g (0.31 mol) of Koyo Pure Chemical Co., Ltd. with a purity of 97% or higher) were added, and 88 g (0.65 mol) of thionyl chloride (95% or higher purity of Wako Pure Chemical Industries) and 0.2 g (0.002 mol) of triethylamine were added. Then, dry argon (dew point −60 ° C. or lower) was introduced at 0.02 liter / min for 60 minutes. Next, the temperature of the vessel was raised to 105 ° C. over 8 hours, and the reaction temperature was maintained for 12 hours. Then, the vessel was cooled to room temperature to obtain 63 g of a reactant A-4 containing bis (chlorosulfonyl) imidic acid.

Next, by drying at 60 ° C. and 1.3 kPa for 3 hours with 72 g (1.24 mol) of lithium fluoride (purity 98% or more, manufactured by Wako Pure Chemical Industries, Ltd.) whose water content became 200 ppm or less, and molecular sieve 1000 g of ethyl acetate (purity 99% or more, manufactured by Wako Pure Chemical Industries) with a water content of 300 ppm or less, 2 g (0.02 mol) of triethylamine (purity 98% or more, manufactured by Wako Pure Chemical) after drying with molecular sieves, the water content was 500 ppm or less ) Was placed in a 2 liter flask, a reflux condenser, a thermometer, a stirrer, and a heating device were set, and dry argon (dew point: −60 ° C. or lower) was introduced at 0.05 liter / min. Next, 61 g of the reactant A-3 was dropped over 2 hours while cooling the solution, and then kept at 25 ° C. for 20 hours. Thereafter, the reaction solution was filtered and concentrated, dissolved in ethanol, and precipitated in methylene chloride to obtain 52 g of white crystals. The resulting white crystals result of infrared spectrum ^{analysis, 845cm -1, 1192cm -1,} identified from the absorption spectrum, etc. 1385Cm ^-1 and bis (fluorosulfonyl) imide lithium, inductively coupled plasma emission spectrometry results, the impurity Chlorine was 5.3 ppm and the yield was 77%.

[ Reference Example 4 ]
30 g (0.31 mol) of sulfamic acid (manufactured by Wako Pure Chemical Industries, Ltd., purity 99.5% or more) was dried with a heat dryer at 50 ° C. for 1 hour, and the water content after drying was 1500 ppm. A 300 ml flask equipped with a reflux condenser, a thermometer, a stirrer, a heating device, and a dry gas introduction tube was dried by heating and cooled to room temperature, and then 30 g (0.31 mol) of dried sulfamic acid, thionyl chloride (Wako Pure) Chlorosulfonic acid (Wako Pure Chemicals purity 97% or more) 36 g (0.31 mol) was added dropwise while charging 100 g (0.74 mol) of pharmaceutical product purity 95% or more) and heating to 50 ° C., and dry nitrogen (dew point) −60 ° C. or less) was introduced at 0.02 liter / minute for 60 minutes. Next, the temperature of the vessel was raised to 100 ° C. over 8 hours, and after maintaining the reaction temperature for 12 hours, the vessel was cooled to room temperature to obtain 60 g of a reactant A-5 containing bis (chlorosulfonyl) imidic acid.

Subsequently, 12 g (0.31 mol) of ammonium fluoride (purity 95% or more, manufactured by Wako Pure Chemical Industries, Ltd.) whose water content was reduced to 1500 ppm or less by drying at 10 mmHg for 3 hours at room temperature was dissolved in 200 g of acetonitrile, and the reaction product A- 5 was neutralized. Furthermore, 40 g (0.69 mol) of potassium fluoride (spray-dried product manufactured by Wako Pure Chemical Industries, Ltd.) whose water content became 200 ppm by drying at 1.3 kPa for 3 hours at 60 ° C., and moisture by drying with molecular sieve. Add 2000 g of acetonitrile (purity 99% or more, manufactured by Wako Pure Chemical Industries) to 300 ppm or less into a 2 liter flask, set a reflux condenser, thermometer, stirrer, and heating device, and dry argon (dew point -60 ° C or less) Was introduced at 0.05 liter / min. Next, the reaction product A-5, which was neutralized while cooling the solution, was added dropwise over 2 hours, and then kept at room temperature for 20 hours. Thereafter, the reaction solution was filtered and concentrated to obtain 54 g of white crystals. The resulting white crystals infrared spectroscopy results ^{845cm -1, 1188cm -1,} identified from the absorption spectrum, etc. 1382Cm ^-1 bis and (fluorosulfonyl) imide potassium, inductively coupled plasma emission spectrometry results, the impurity chlorine Was 6.5 ppm, and the yield was 80%.

[Example 2 ]
30 g (0.31 mol) of sulfamic acid (purity 99.5% or more manufactured by Wako Pure Chemical Industries, Ltd.) was dried for 3 hours under a reduced pressure of 1.3 kPa with a vacuum dryer at 60 ° C., and the water content after drying was 150 ppm. It was. A 500 ml flask equipped with a reflux condenser, a thermometer, a stirrer, a heating device, and a dry gas introduction tube was dried by heating and cooled to room temperature, then 30 g (0.31 mol) of dried sulfamic acid, thionyl chloride (Wako Pure) 88 g (0.65 mol) of drug product purity 95% or more and 36 g (0.31 mol) of chlorosulfonic acid (purity 97% or more product of Wako Pure Chemical Industries) were charged, and dry nitrogen (dew point -60 ° C. or less) was set to 0.00. Introduced at 05 liters / minute for 60 minutes. Next, the temperature of the container was raised to 130 ° C. over 8 hours, and after maintaining the reaction temperature for 1 hour, it was cooled to room temperature to obtain 65 g of bis (chlorosulfonyl) imidic acid.

Next, 72 g (1.24 mol) of potassium fluoride (spray-dried product manufactured by Wako Pure Chemical Industries, Ltd.) whose water content became 200 ppm by drying at 1.3 kPa for 3 hours at 60 ° C. and the molecular sieve were used to dry the water. 1 liter (0.01 mol) of pyridine (purity 99% or more, manufactured by Wako Pure Chemical Industries, Ltd.) having a moisture content of 500 ppm after being dried with molecular sieves and 1500 g of acetonitrile (purity 99% or more, manufactured by Wako Pure Chemical Industries) The flask was placed, a reflux condenser, a thermometer, a stirring device, and a heating device were set, and dry nitrogen (dew point: −60 ° C. or lower) was introduced at 0.05 liter / min. Next, 65 g of bis (chlorosulfonyl) imidic acid was added dropwise over 2 hours while cooling the solution, and then kept at a temperature of 40 ° C. for 12 hours. Thereafter, the reaction solution was filtered and concentrated to obtain 61 g of white crystals. The resulting white crystals result of infrared spectrum ^{analysis, 845cm -1, 1188cm -1,} identified from the absorption spectra of such 1382Cm ^-1 bis and (fluorosulfonyl) imide potassium, electromagnetic induction plasma emission analysis (ICP analysis) As a result, the impurity chlorine was 55 ppm, and the yield was 96%.

[ Reference Example 5 ]
30 g (0.31 mol) of sulfamic acid (purity 99.5% or more manufactured by Wako Pure Chemical Industries, Ltd.) was dried at 6.7 kPa for 1 hour at room temperature, and the moisture after drying was 3000 ppm. A 300 ml flask equipped with a reflux condenser, a thermometer, a stirrer, a heating device, and a dry gas introduction tube was dried by heating and cooled to room temperature, and then 30 g (0.31 mol) of dried sulfamic acid, thionyl chloride (Wako Pure) 150 g (1.11 mol) of purity 95% or more manufactured by Yakuhin, 40 g (0.34 mol) of chlorosulfonic acid (purity 97% or more by Wako Pure Chemical Industries) were added dropwise, and dry nitrogen (dew point -60 ° C or less) was 0. After introduction at 0.02 liter / min, 1 g (0.03 mol) of triethylamine was added. Next, the vessel was heated to 140 ° C. over 12 hours and maintained at the reaction temperature for 1 hour, and then cooled to room temperature to obtain 60 g of a reactant A-7 containing bis (chlorosulfonyl) imidic acid.

Next, 160 g (2.75 mol) of potassium fluoride (spray-dried product manufactured by Wako Pure Chemical Industries, Ltd.) whose water content was 200 ppm by drying at 1.3 kPa for 3 hours at 60 ° C. was stirred in dry nitrogen. The reaction product A-7 was added dropwise over 2 hours and mixed. Next, the reaction product was washed with 2000 g of acetonitrile (0.05% or more by Wako Pure Chemical Industries, Ltd.) containing 0.05 g (0.0006 mol) of pyridine, and the filtrate was filtered and concentrated to obtain 50 g of white crystals. The resulting white crystals infrared spectroscopy results ^{845cm -1, 1188cm -1,} identified from the absorption spectrum, etc. 1382Cm ^-1 bis and (fluorosulfonyl) imide potassium, inductively coupled plasma emission spectrometry results, the impurity chlorine Was 2.5 ppm and the yield was 81%.

[Example 3 ]
30 g (0.31 mol) of sulfamic acid (purity 99.5% or more, manufactured by Wako Pure Chemical Industries, Ltd.) 50 g, thionyl chloride in a 300 ml flask equipped with a reflux condenser, thermometer, stirring device, heating device, and dry gas introduction tube (Wako Pure Chemicals purity 95% or more) 100g (0.74mol), chlorosulfonic acid (Wako Pure Chemicals purity 97% or more) 36g (0.31mol) was charged, dry nitrogen (dew point -60 ℃ or less) Was introduced at 0.02 liter / min for 60 minutes, and then the vessel was heated to 120 ° C. over 6 hours and maintained at 120 ° C. for 4 hours. Thereafter, the reaction product is cooled, 30 g (0.4 mol) of potassium chloride (purity 99.5% or more manufactured by Wako Pure Chemical Industries, Ltd.) is added, hydrochloric acid gas is driven off, and the reaction product A- containing potassium bis (chlorosulfonyl) imide is added. 70 g of 8 was obtained.

Next, 72 g (1.24 mol) of potassium fluoride (spray-dried product manufactured by Wako Pure Chemical Industries, Ltd.) whose water content became 200 ppm by drying at 1.3 kPa for 3 hours at 60 ° C. and the molecular sieve were used to dry the water. 2 liters of 1,500 g of ethyl acetate (purity 99% or higher, manufactured by Wako Pure Chemical), 100 ppm, and 1 g (0.01 mole) of pyridine (purified 99% or higher, manufactured by Wako Pure Chemical), dried with molecular sieves and having a water content of 500 ppm The reflux condenser, thermometer, stirring device, and heating device were set, and dry nitrogen (dew point: −60 ° C. or lower) was introduced at 0.05 liter / min. Next, 65 g of bis (chlorosulfonyl) imidic acid was added dropwise over 2 hours while cooling the solution, and then the temperature was maintained at 60 ° C. for 6 hours. Thereafter, the reaction solution was filtered and concentrated to obtain 61 g of white crystals. The resulting white crystals result of infrared spectrum ^{analysis, 845cm -1, 1188cm -1,} identified from the absorption spectrum, etc. 1382Cm ^-1 bis and (fluorosulfonyl) imide potassium, the result of electromagnetic induction plasma emission spectrometry (ICP analysis) The impurity chlorine was 55 ppm, and the yield was 95%.

[Comparative Example 1]
In a 200 ml flask equipped with a reflux condenser, a thermometer, a stirrer, a heating device, and a dry gas introduction tube, 6 g (0.10 mol) of urea (purity 99% or more manufactured by Wako Pure Chemical Industries), thionyl chloride (Wako Pure Chemical Industries, Ltd.) 50 g (0.41 mol) (purity 95% or higher) was charged, and 40 g (0.40 mol) of fluorosulfonic acid (purity 97% or higher, manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise with care in handling. After completion of the dropwise addition, dry nitrogen (dew point −60 ° C. or lower) was introduced at 0.05 liter / min, the temperature was slowly raised to 110 ° C., and maintained at 110 ° C. for 4 hours to obtain a reaction product B-1.

Next, pulverized potassium fluoride (35 g, 0.47 mol) was placed in a 500 ml flask, 200 ml of methylene chloride was added, and the reaction product B-1 was dissolved in 100 ml of methylene chloride and added into the flask. The mixture was stirred for 3 hours at room temperature and then heated to 150 ° C. while distilling off the solvent. After cooling, the IR spectrum of the dried product in the flask was measured, and a peak of potassium bis (fluorosulfonyl) imide was observed. 100 ml of tetrahydrofuran was added to the dried solid, filtered, and then added dropwise to methylene chloride to obtain 17 g of a dark brown solid. This crystal was found to be a mixture containing potassium bis (fluorosulfonyl) imide from the IR spectrum. The IR spectrum ^845cm -1, purity by analogy from the peak and the peak of the other impurities 1188Cm ^-1 is estimated to less than 50%, and the yield was estimated to about 30% or less.

  Examples of utilization of the bis (fluorosulfonyl) imide compound according to the present invention include device materials such as battery electrolytes and ionic liquids, production of pharmaceutical intermediates, and applications such as lubricating oil and heat medium.

Claims (2)

A method for producing a bis (fluorosulfonyl) imide anion compound comprising a reaction of fluorinating a bis (chlorosulfonyl) imide anion compound obtained from sulfamic acid, chlorosulfonic acid and a halogenating agent with a fluoride salt,
0.95 to 1.05 mol of the chlorosulfonic acid is used per 1 mol of sulfamic acid,
The halogenating agent is used in an amount of 2.0 to 4.0 mol with respect to 1 mol of sulfamic acid,
In the reaction of substituting the bis (chlorosulfonyl) imide anion compound with fluorine, 3.0 to 4.0 mol of potassium fluoride is used as a fluoride salt with respect to 1 mol of bis (chlorosulfonyl) imidic acid, or bis Using 2.0 to 4.0 moles per mole of (chlorosulfonyl) imidoate, and using a nitrogen-containing compound as a base catalyst for 1 mole of bis (chlorosulfonyl) imidic acid or bis (chlorosulfonyl) imidate A method for producing a bis (fluorosulfonyl) imide anion compound, characterized by using 0.03 to 0.06 mol. In the reaction of substituting the bis (chlorosulfonyl) imide anion compound with fluorine, one or more selected from acetonitrile, N, N-dimethylformamide, tetrahydrofuran, dioxane, and ethyl acetate are used as a solvent, and The method for producing a bis (fluorosulfonyl) imide anion compound according to claim 1, wherein the reaction temperature is 5 to 70 ° C.