JP6394242B2 - Method for producing difluoroionic complex - Google Patents

Description

  The present invention relates to an additive added to an electrolytic solution and a supporting electrolyte for the electrolytic solution in order to protect the electrode surface of an electrochemical device such as a lithium ion battery, a sodium ion battery, a lithium air battery, a lithium sulfur battery, and a lithium ion capacitor. The present invention relates to a method for producing a difluoroionic complex used as the above.

  In the battery that is an electrochemical device, in recent years, information-related equipment, communication equipment, that is, personal computers, video cameras, digital cameras, mobile phones, smart phones and other small-sized, high energy density power storage systems, electric vehicles, hybrid vehicles, Storage systems for large and power applications such as fuel cell vehicle auxiliary power supplies and power storage are attracting attention. Non-aqueous electrolyte batteries such as lithium ion batteries, lithium batteries, and lithium ion capacitors have been actively developed as one candidate.

  Many of these non-aqueous electrolyte batteries have already been put into practical use, but their electric capacity is reduced by repeated charging and discharging at low temperatures or exposure to high temperature environments. For these reasons, the performance of non-aqueous electrolyte batteries is sufficient in applications that require use in a low temperature environment of about minus 30 ° C., a high temperature environment of about 60 ° C., or for a long period of several years, such as automobile power supplies. It can not be said.

  In the case of a lithium ion battery, when lithium cations are inserted into the negative electrode during the initial charge, the negative electrode and the lithium cation, or the negative electrode and the electrolyte solvent react, and lithium oxide, lithium carbonate, and alkyl lithium carbonate are mainly formed on the negative electrode surface. A coating film as a component is formed. The film on the electrode surface is called Solid Electrolyte Interface (SEI), and its properties have a great influence on the battery performance, such as suppressing the decomposition of the solvent and suppressing the deterioration of the battery performance.

  In order to suppress a decrease in electric capacity due to low temperature, high temperature, or repeated charge / discharge, it is important to form SEI that has high ion conductivity and low electron conductivity and is stable over a long period of time. It is. Therefore, a small amount (usually 0.01% by mass or more and 10% by mass or less) of a compound called an additive is added to the electrolytic solution, and a part or all of the compound is decomposed at the time of initial charging. There have been extensive attempts to form SEI.

For example, in Patent Document 1, vinylene carbonate is used. In Patent Document 2, unsaturated cyclic sulfonic acid esters such as 1,3-propene sultone are used. In Patent Document 3, carbon dioxide is used. In Patent Document 4, 1,2,3, Aromatic compounds such as 4-tetrahydronaphthalene, nitrogen-containing unsaturated compounds such as pyridine in Patent Document 5, lithium bisoxalatoborate in Patent Document 6, and oxalic acid as a ligand in Patent Document 7 A mixture of a difluoroionic acid complex having a tetrafluoroionic complex and tetrafluoroionic complex is used as an additive for forming effective SEI.

  In addition, metal salts (Li, Na, etc.) of ionic complexes in which Lewis acid and fluorine ions are bonded, such as hexafluorophosphate anion, tetrafluoroborate anion and hexafluoroarsenate anion, have high solubility and high ion. From the standpoint of dissociation and wide potential window, it is used as a supporting electrolyte for electrolytes of electrochemical devices.

Among them, lithium hexafluorophosphate (hereinafter LiPF ₆ ) is particularly widely used because it is less toxic than lithium hexafluoroarsenate and has higher solubility than lithium tetrafluoroborate.

However, this LiPF ₆ also has a major drawback in that it has low thermal stability and decomposes into lithium fluoride (hereinafter LiF) and phosphorus pentafluoride (hereinafter PF ₅ ) by heating. LiF accumulates on the electrode surface and becomes a resistance component, thereby reducing the performance of lithium-based electrochemical devices such as lithium ion batteries, and PF ₅ accelerates the decomposition of the electrolyte solvent from its strong Lewis acidity. Are known.

Therefore, less toxic than hexafluoroarsenate, soluble than lithium tetrafluoroborate is high, LiPF ₆ Development of thermal stability is high ionic complex has been actively than, for example, a part of fluorine LiPF ₆ The use of an ionic complex in which a fluoroalkyl group (CF ₃ , C ₂ F ₅ ) is replaced is disclosed in Patent Document 8, and the use of an ionic complex in which a part or all of the fluorine of LiPF ₆ is replaced with oxalic acid is disclosed in Patent Document 8. 9 and disclosed in Non-Patent Documents 1 and 2.

 As described above, among ionic complexes used as an additive to be added to the electrolyte solution to protect the electrode surface of the electrochemical device or as a supporting electrolyte for the electrolyte solution, the difluoroionic complex is particularly excellent. However, recent research has revealed this.

JP-A-8-045545 (Japanese Patent No. 3573521) JP 2002-329528 (Patent No. 4190162) JP 7-176323 A Japanese Patent Laid-Open No. 2003-007334 (Patent No. 3417411) JP 2003-115324 A JP 2007-335143 A JP 2011-222193 (Patent No. 5573313) JP 2003-17118 A JP 2002-110235 (Patent No. 3722585) JP 2003-137890 (Patent 3907446)

ECS Transactions 2009, 16 (35), 3-11 Chem. Eur. J. 2004, 10, 2451-2458

A difluoroionic complex having phosphorus as a central element and oxalic acid as a ligand is disclosed in Patent Document 10, and LiPF ₆ and oxalic acid are mixed with a reaction aid such as SiCl ₄ , BCl _3, or AlCl ₃ . It is produced by reacting in the presence. Oxalic acid is coordinated to phosphorus while removing F from LiPF ₆ by utilizing the fact that Si, B, or Al contained in the reaction aid forms a strong bond with F. Here, LiPF ₆ The removed F is in a state that must be discarded. That is, since the Si-F, BF, and Al-F bonds are strong, a large amount of energy is required to cut the bonds and recover and reuse the F. I had to.

Further, LiPF ₆ as a raw material is manufactured by fluorinating a raw material not containing fluorine such as phosphorus trichloride or phosphorus pentachloride. In the process of synthesizing a difluoroionic complex, it is essential to remove four molecules of fluorine from LiPF ₆ and then coordinate two molecules of bidentate ligands. To remove fluorine once bound to phosphorus Thus, the fluorine utilization efficiency is extremely low.

  The use of reaction aids as described above, disposal / detoxification treatment of removed fluorine (fluoride of Si, B, Al), and low use efficiency of fluorine only contribute to an increase in manufacturing costs. In order to protect the electrode surface of the electrochemical device, the reaction aid or the reaction product of the reaction aid and the raw material ligand remains in the reaction solution as a residual chlorine component. When used as an additive added to the electrolyte or as a supporting electrolyte for the electrolyte, the residual chlorine component causes corrosion of electrochemical device components, does not use reaction aids, and uses fluorine A highly efficient synthesis method has been strongly desired.

  The present invention has been made in view of the above circumstances, and provides a method for producing a difluoroionic complex having not only a small amount of waste with high fluorine utilization efficiency but also a small amount of residual chlorine component without using a reaction aid. For the purpose.

  The present inventor has made extensive studies to solve the above problems, and selectively fluorinated a hexacoordinate ionic complex in which three molecules of a bidentate ligand are coordinated. The inventors have found that this can be solved, and have completed the present invention. Specifically, the present invention provides the following.

The present invention relates to a hexacoordinate ionic complex in which three molecules of a bidentate ligand represented by the following general formula (1) are coordinated with acidic potassium fluoride, acidic sodium fluoride, acidic ammonium fluoride, fluoride Production of a difluoroionic complex represented by the following general formula (2) including a step of introducing fluorine with one or more fluorinating agents selected from the group consisting of hydrogen-rich organic amine hydrogen fluoride salts and hydrogen fluoride Provide a method.

In the general formulas (1) and (2), A ⁺ is any one selected from the group consisting of metal ions, protons and onium ions, and M is any one selected from the group consisting of P, As and Sb. One. F is a fluorine atom. O is an oxygen atom.
Y is a carbon atom or a sulfur atom. Q is 1 when Y is a carbon atom. Q is 1 or 2 when Y is a sulfur atom.
W is a hydrocarbon group that may have a heteroatom having 1 to 10 carbon atoms and / or a halogen atom (in the case where the number of carbon atoms is 3 or more, a branched chain or cyclic structure can also be used), Or -N (R < ¹ >)-is represented. In this case, R ¹ represents a hydrogen atom, an alkali metal, hydrocarbon group which may have a hetero atom and / or a halogen atom having 1 to 10 carbon atoms. When the number of carbon atoms is 3 or more, R ¹ can take a branched chain or a cyclic structure. Z is a carbon atom. p is 0 or 1, q is an integer of 0 to 2, r is an integer of 0 to 2, s represents 0 or 1, and p + r ≧ 1. However, when s is 0, there is no oxygen atom double-bonded to Z.

It is preferable that each element of the anion portion of the hexacoordinate ionic complex (1) and the difluoroionic complex (2) is at least one combination selected from (a), (b), and (c).
(A) M = P, Y = C, p, q, s = 1, r = 0
(B) M = P, W = C (CF ₃ ) ₂ , p, q = 0, r, s = 1
(C) M = P, W = C (CF ₃ ) ₂ , p, q, s = 0, r = 2

  The fluorinating agent is preferably an ionic fluoride, and the fluorinating agent is acidic potassium fluoride, acidic sodium fluoride, acidic ammonium fluoride, hydrogen fluoride-excess organic amine hydrogen fluoride salt, hydrogen fluoride. It is preferably at least one selected from the group consisting of Moreover, it is preferable that the equivalent of the said fluorinating agent is 1.5 to 50 molar equivalent with respect to the said six coordination ionic complex (1).

  In particular, the fluorinating agent preferably contains hydrogen fluoride, and the equivalent of hydrogen fluoride as the fluorinating agent is preferably 1.5 to 50 molar equivalents relative to the six-coordinate ionic complex (1). .

In the present invention, the six-coordinated ionic complex (1) represented by the general formula (1) is an organic solution containing potassium acid fluoride, sodium acid fluoride, ammonium acid fluoride, excess hydrogen fluoride in a non-aqueous solvent. Amine hydrogen fluoride, hydrogen fluoride, potassium fluoride, sodium fluoride, lithium fluoride, cesium fluoride, nickel fluoride, calcium fluoride, antimony fluoride, iron fluoride, zinc fluoride, manganese fluoride, fluorine A method of fluorinating with one or more fluorinating agents selected from the group consisting of ytterbium fluoride, hafnium fluoride, cobalt fluoride, ammonium fluoride, tetrabutylammonium fluoride, and at the time of fluorination, sulfuric acid, fluorosulfuric acid , Hydrogen chloride, methanesulfonic acid, trifluoromethanesulfonic acid, trifluoroacetic acid, nitric acid, p-toluenesulfo Non-aqueous solvent for acid or Lewis acid other than one or more fluorinating agents selected from the group consisting of acid, boron trifluoride, phosphorus pentafluoride, aluminum trichloride, niobium pentachloride, metal trifluoromethanesulfonate A method for producing a difluoroionic complex represented by the general formula (2) to be added to the above is provided. It is preferable that the equivalent of an acid or Lewis acid other than the fluorinating agent is 0.001 to 2.0 molar equivalents relative to the hexacoordinate ionic complex (1).

  In particular, the acid other than the fluorinating agent is one or more selected from the group consisting of trifluoromethanesulfonic acid, methanesulfonic acid, and trifluoroacetic acid, and the equivalent of the acid other than the fluorinating agent is the 6-coordinated ionicity. It is preferable that it is 0.001-2.0 molar equivalent with respect to a complex (1). The fluorinating agent is preferably hydrogen fluoride, and the acid other than the fluorinating agent is preferably one or more selected from the group consisting of trifluoromethanesulfonic acid, methanesulfonic acid, and trifluoroacetic acid.

  An acid other than the fluorinating agent or Lewis acid is added at the time of fluorination, and lithium fluoride, sodium fluoride, potassium fluoride, cesium fluoride, calcium fluoride, nickel fluoride, iron fluoride are added to the fluorinating agent. Preferably, at least one selected from the group consisting of zinc fluoride and ammonium fluoride is included.

  The non-aqueous solvent is preferably one selected from the group consisting of carbonates, esters, ketones, lactones, ethers, nitriles, amides, sulfones, or a mixture thereof. Solvent is dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, butyl propionate, acetone, ethyl methyl ketone, diethyl ketone, γ-butyrolactone, γ-valerolactone, tetrahydrofuran, tetrahydropyran, dibutyl ether, diisopropyl ether, 1,2-dimethoxyethane, 1,2-diethoxyethane, acetonitrile, propionitrile, N, N-dimethylformamide, dimethylsulfo One selected from the group consisting of xoxide and sulfolane, or a mixture thereof is preferable.

  The fluorination is preferably performed at a temperature of −60 ° C. to 150 ° C., and it is preferable to perform a decompression operation after the fluorination. In particular, the ligand of the six-coordinated ionic complex (1) and the difluoroionic complex (2) is oxalic acid, and the oxalic acid that has precipitated in the pressure reduction operation after fluorination is separated by filtration. Is preferred.

The present invention uses a conventional reaction aid such as SiCl ₄ , BCl _3, or AlCl ₃ by selectively fluorinating a six-coordinate ionic complex in which three molecules of a bidentate ligand are coordinated. Therefore, there is no need to dispose of fluorine that has reacted with the reaction aid, and not only waste is reduced due to high fluorine utilization efficiency, but also a difluoroionic complex with little residual chlorine component because no reaction aid containing chlorine is used. The manufacturing method of can be provided.

  Hereinafter, the present invention will be described in more detail.

  The present invention relates to a hexacoordinate ionic complex in which three molecules of a bidentate ligand represented by the following general formula (1) are coordinated (hereinafter sometimes referred to as a hexacoordinate ionic complex (1)). This is a method for producing a difluoroionic complex represented by the following general formula (2) (hereinafter sometimes referred to as difluoroionic complex (2)), including a step of introducing fluorine.

In the general formulas (1) and (2), A ⁺ is any one selected from the group consisting of metal ions, protons and onium ions, and serves to assist ion conduction in the nonaqueous electrolyte battery. From the viewpoint, lithium ion, sodium ion, potassium ion, or quaternary alkyl ammonium ion is preferable. Although it does not specifically limit as a quaternary alkylammonium ion, For example, a trimethylpropyl ammonium and 1-butyl-1-methylpyrrolidinium are mentioned.

In the general formulas (1) and (2), M is any one selected from the group consisting of P, As and Sb. F is a fluorine atom. O is an oxygen atom.
Y is a carbon atom or a sulfur atom. Q is 1 when Y is a carbon atom. Q is 1 or 2 when Y is a sulfur atom.
W is a hydrocarbon group that may have a heteroatom having 1 to 10 carbon atoms and / or a halogen atom (in the case where the number of carbon atoms is 3 or more, a branched chain or cyclic structure can also be used), Or -N (R < ¹ >)-is represented. In this case, R ¹ represents a hydrogen atom, an alkali metal, hydrocarbon group which may have a hetero atom and / or a halogen atom having 1 to 10 carbon atoms. When the number of carbon atoms is 3 or more, R ¹ can take a branched chain or a cyclic structure. Z is a carbon atom. p is 0 or 1, q is an integer of 0 to 2, r is an integer of 0 to 2, s represents 0 or 1, and p + r ≧ 1. However, when s is 0, there is no oxygen atom double-bonded to Z.

It is preferable that each element of the anion portion of the hexacoordinate ionic complex (1) and the difluoroionic complex (2) is at least one combination selected from (a), (b), and (c).
(A) M = P, Y = C, p, q, s = 1, r = 0 Oxalic acid (b) M = P, W = C (CF ₃ ) ₂ , p, q = 0, r, s = 1 hexafluorohydroxyisobutyric acid (c) M = P, W = C (CF ₃ ) ₂ , p, q, s = 0, r = 2 perfluoropinacol

  After dissolving or suspending the 6-coordinating ionic complex (1) in a non-aqueous solvent, a fluorinating agent having a molar ratio of 1.5 to 50 moles to the 6-coordinated ionic complex (1) is added. The difluoroionic complex (2) is obtained by selective fluorination with use. At this time, the amount of the fluorinating agent used is preferably 1.8 to 40 mol times, more preferably 2.0 to 20 mol times.

  As a fluorinating agent, an ionic fluorinating agent that generates fluoride ions when added to a non-aqueous solvent can be used. Among them, acidic potassium fluoride, acidic sodium fluoride, acidic ammonium fluoride, hydrogen fluoride Acidic substances such as excess organic amine hydrogen fluoride and hydrogen fluoride are preferred, and hydrogen fluoride is more preferred because of its high reaction rate.

  At the time of fluorination, an acid or a Lewis acid may be added in addition to the fluorinating agent. By adding an acid or a Lewis acid, the reaction rate at the time of introducing fluorine using a fluorinating agent can be improved. Here, sulfuric acid, fluorosulfuric acid, hydrogen chloride, methanesulfonic acid, trifluoromethanesulfonic acid, trifluoroacetic acid, nitric acid, p-toluenesulfonic acid can be used as an acid (protic acid or Bronsted acid) other than the fluorinating agent. As a Lewis acid other than the fluorinating agent, boron trifluoride, phosphorus pentafluoride, aluminum trichloride, niobium pentachloride, trifluoromethanesulfonic acid metal salt (cations are Li, Na, K, La, Ce, Pr, Nd Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y) can be used. In particular, it is preferable to use trifluoromethanesulfonic acid, methanesulfonic acid, or trifluoroacetic acid because the effect of improving the reaction rate is great.

  The equivalent of the acid other than the fluorinating agent or the Lewis acid is preferably 0.001 to 2.0 molar equivalents relative to the hexacoordinate ionic complex (1). If the amount of the acid other than the fluorinating agent or the Lewis acid is too small, the effect of improving the reaction rate is small. If the amount is too large, not only the cost increases but also the decomposition of the product proceeds.

  By adding an acid or Lewis acid, it is possible to use other than the above acidic fluorinating agent. In this case, potassium fluoride, sodium fluoride, lithium fluoride, cesium fluoride, nickel fluoride, Calcium fluoride, antimony fluoride, iron fluoride, zinc fluoride, manganese fluoride, ytterbium fluoride, hafnium fluoride, cobalt fluoride, ammonium fluoride, tetrabutylammonium fluoride, etc. are used, especially potassium fluoride , Sodium fluoride, lithium fluoride, cesium fluoride, calcium fluoride, nickel fluoride, cobalt fluoride, iron fluoride, zinc fluoride, manganese fluoride, and ammonium fluoride are preferable. To lithium fluoride, sodium fluoride, potassium fluoride, cesium fluoride, calcium fluoride Beam, nickel fluoride, iron fluoride, zinc fluoride, ammonium fluoride is preferred.

  The non-aqueous solvent used in the synthesis method described above dissolves the 6-coordinate ionic complex (1) as a raw material even in a very small amount, and does not cause a reaction with a compound in the system. Those having a relative dielectric constant of 2 or more are preferable. Here, when a non-aqueous solvent having no solubility is used, it is not preferable because fluorination becomes very slow. If there is even a slight solubility, the reaction proceeds because the solubility of the target difluoroionic complex (2) is high. For example, carbonate esters, esters, ketones, lactones, ethers, nitriles, amides, sulfones and the like can be used, and not only a single solvent but also two or more kinds of mixed solvents may be used.

  Specific examples of the non-aqueous solvent include dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, butyl propionate, acetone, ethyl Methyl ketone, diethyl ketone, γ-butyrolactone, γ-valerolactone, tetrahydrofuran, tetrahydropyran, dibutyl ether, diisopropyl ether, 1,2-dimethoxyethane, 1,2-diethoxyethane, acetonitrile, propionitrile, N, N -Dimethylformamide, dimethyl sulfoxide, sulfolane and the like. Among them, a solvent having a boiling point of 120 ° C or lower is preferable, and dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, ethyl acetate, methyl propionate, propylene More preferred are ethyl lopionate, acetone, tetrahydrofuran, 1,2-dimethoxyethane, and acetonitrile.

  The reaction temperature at the time of introducing fluorine using a fluorinating agent is −60 ° C. to 150 ° C., preferably −20 to 120 ° C. Fluorine introduction does not proceed sufficiently at temperatures lower than −60 ° C., and decomposition of the 6-coordinate ionic complex (1) or difluoroionic complex (2) that is a product may occur at temperatures above 150 ° C. There is sex. The range of −20 to 120 ° C. is optimal in order to obtain a sufficient fluorine introduction rate and not cause decomposition.

  The reaction time can be appropriately selected according to the reaction rate. However, since occupying the apparatus for a long time leads to an increase in production cost, it is actually preferable to set it to 72 hours or less. Furthermore, in order to advance the reaction of the entire system, it is preferable to stir the solution during the reaction.

  After fluorination, it is preferable to perform a pressure reduction operation to reduce the residual free acid concentration, and if necessary, remove the precipitate by filtration. At this time, since a part of the non-aqueous solvent is also distilled off, the concentration of the product difluoroionic complex (2) is concentrated. A vacuum pump, an aspirator, etc. can be used for pressure reduction operation. The depressurization operation is carried out by keeping the reactor in a sealed state and then maintaining the system at a pressure below atmospheric pressure. Since the pressure in the system varies depending on the temperature and vapor pressure of the liquid to be purified, it cannot be generally stated. However, it is preferable to maintain the vacuum in the tank at 80 kPa or less in absolute pressure. If the pressure to be maintained exceeds 80 kPa, it takes a long time to eliminate the residual free acid concentration until it becomes a desired concentration or less. Moreover, since the decomposition reaction product and the unreacted purification agent can be excluded to a low concentration, it is further preferable that the pressure to be maintained is 50 kPa or less. In view of the burden on the apparatus, the absolute pressure is preferably 20 kPa or more. In particular, when the ligand of the six-coordinated ionic complex (1) and the difluoroionic complex (2) is oxalic acid, a pressure reduction operation is performed after fluorination, and a part of the solvent is distilled off to difluoro It is preferable to separate the oxalic acid deposited when the ionic complex (2) is concentrated by filtration.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited by the Example which concerns.

  In either case, the raw materials and products were handled in a nitrogen atmosphere having a dew point of −50 ° C. or less. The glass reactor and fluororesin reactor used were those dried at 150 ° C. for 12 hours or more and then cooled to room temperature under a nitrogen stream having a dew point of −50 ° C. or less.

[Example 1-1]
According to the method disclosed in Non-Patent Document 2, lithium trisoxalatophosphate (1a-Li), which is a hexacoordinate ionic complex in which three molecules of oxalic acid are coordinated, was obtained. (1a-Li) (30 g, 99.4 mmol) is added to a 500 mL fluororesin reactor, and ethyl methyl carbonate (hereinafter EMC) (120 mL) is added and dissolved as a non-aqueous solvent. Hydrogen fluoride (hereinafter HF) (3.6 g, 178.8 mmol, 1.8 molar equivalent) was added. After stirring at 25 ° C. for 24 hours, the pressure was reduced to 50-80 kPa at 25 ° C. to remove residual HF, and at the same time, part of the nonaqueous solvent was distilled off to concentrate the ionic complex. . After removing the precipitated oxalic acid by filtration, the conversion rate and selectivity were determined by F, P-NMR, the residual chlorine concentration by silver nitrate titration, and the residual free acid concentration by free acid titration. The conversion rate to a difluoroionic complex (2a-Li) in which oxalic acid is coordinated to 25.0% and selectivity is 98.0%. The residual chlorine concentration and the residual free acid concentration are difluoroionic. They were less than 100 ppm by mass and 2000 ppm by mass, respectively, based on the complex (2a-Li).
Conversion rate [%] = Target product mol%
Selectivity [%] = conversion rate / (100−mol% of residual raw material) × 100

[Example 1-2]
As a result of carrying out the reaction in the same procedure as Example 1-1 except that the addition amount of HF was changed to (4.0 g, 198.7 mmol, 2.0 molar equivalents), the difluoroionic complex (2a-Li) The conversion rate to 29.6% and the selectivity were 93.4%, and the residual chlorine concentration and the residual free acid concentration were less than 100 ppm by mass and 2000 masses, respectively, based on the difluoroionic complex (2a-Li). ppm.

[Example 1-3]
As a result of performing the reaction in the same procedure as in Example 1-2 except that the reaction time was changed from 24 hours to 72 hours, the conversion rate to the difluoroionic complex (2a-Li) was 37.7%, and the selectivity The residual chlorine concentration and the residual free acid concentration were respectively less than 100 ppm by mass and 2000 ppm by mass based on the difluoroionic complex (2a-Li).

[Example 1-4]
As a result of performing the reaction in the same procedure as in Example 1-3 except that the temperature was changed from 25 ° C. to 40 ° C., the conversion rate to the difluoroionic complex (2a-Li) was 50.5%, and the selectivity was The residual chlorine concentration and the residual free acid concentration were respectively less than 100 ppm by mass and 2000 ppm by mass based on the difluoroionic complex (2a-Li).

[Example 1-5]
As a result of performing the reaction in the same procedure as in Example 1-2 except that the temperature was changed from 25 ° C. to 80 ° C., the conversion rate to the difluoroionic complex (2a-Li) was 51.3%, and the selectivity was The residual chlorine concentration and the residual free acid concentration were respectively less than 100 ppm by mass and 2000 ppm by mass based on the difluoroionic complex (2a-Li).

[Example 1-6]
As a result of carrying out the reaction in the same procedure as Example 1-1 except that the addition amount of HF was changed to (11.9 g, 596.2 mmol, 6.0 molar equivalent), the difluoroionic complex (2a-Li) The conversion rate to 71.0% and the selectivity is 95.4%, and the residual chlorine concentration and residual free acid concentration are less than 100 ppm by mass and 2000 masses, respectively, based on the difluoroionic complex (2a-Li). ppm.

[Example 1-7]
As a result of carrying out the reaction in the same procedure as in Example 1-6 except that the reaction time was changed from 24 hours to 48 hours, the conversion rate to the difluoroionic complex (2a-Li) was 90.0%, and the selectivity The residual chlorine concentration and the residual free acid concentration were respectively less than 100 ppm by mass and 2000 ppm by mass based on the difluoroionic complex (2a-Li).

[Example 1-8]
As a result of carrying out the reaction by the same procedure as Example 1-1 except that the addition amount of HF was changed to (19.9 g, 993.6 mmol, 10.0 molar equivalent), the difluoroionic complex (2a-Li) The conversion rate is 92.3% and the selectivity is 93.2%. The residual chlorine concentration and the residual free acid concentration are less than 100 ppm by mass and 2000 masses, respectively, based on the difluoroionic complex (2a-Li). ppm.

[Example 1-9]
As a result of carrying out the reaction in the same procedure as in Example 1-1, except that the addition amount of HF was changed to (39.7 g, 1987.2 mmol, 20.0 molar equivalents) and the reaction time was changed to 3 hours, difluoro ion The conversion rate to the functional complex (2a-Li) is 93.4% and the selectivity is 94.3%. The residual chlorine concentration and the residual free acid concentration are based on the difluoroionic complex (2a-Li), respectively. It was less than 100 mass ppm and 4000 mass ppm. When 30 mL of EMC was added and 30 mL of the additional portion was distilled off again by concentration under reduced pressure, the residual free acid concentration decreased to 2000 ppm by mass.

[Example 1-10]
As a result of carrying out the reaction in the same procedure as in Example 1-1, except that the addition amount of HF was changed to (79.5 g, 3984.4 mmol, 40.0 molar equivalent) and the reaction time was changed to 1 hour, difluoro ion The conversion rate to the functional complex (2a-Li) is 91.0% and the selectivity is 95.0%. The residual chlorine concentration and the residual free acid concentration are based on the difluoroionic complex (2a-Li), respectively. It was less than 100 mass ppm and 7000 mass ppm. When 30 mL of EMC was added and 30 mL of the additional portion was distilled off again by concentration under reduced pressure, the residual free acid concentration decreased to 3000 ppm by mass.

[Example 1-11]
As a result of carrying out the reaction in the same procedure as Example 1-1 except that the fluorinating agent was changed to triethylamine hydrogen trifluoride (32.0 g, 198.7 mmol, 2.0 molar equivalent), a difluoroionic complex was obtained. The conversion rate to (2a-Li) is 21.2%, the selectivity is 91.2%, and the residual chlorine concentration and the residual free acid concentration are 100 masses each based on the difluoroionic complex (2a-Li). It was less than ppm and 6000 mass ppm. When 30 mL of EMC was added and 30 mL of the additional portion was distilled off again by concentration under reduced pressure, the residual free acid concentration decreased to 3000 ppm by mass.

[Example 1-12]
As a result of carrying out the reaction in the same procedure as Example 1-1 except that the fluorinating agent was changed to triethylamine hydrogen trifluoride (96.1 g, 596.2 mmol, 6.0 molar equivalent), a difluoroionic complex was obtained. The conversion rate to (2a-Li) is 63.1%, the selectivity is 83.5%, and the residual chlorine concentration and the residual free acid concentration are 100 masses each based on the difluoroionic complex (2a-Li). It was less than 1ppm and 15000 mass ppm. When 30 mL of EMC was added and 30 mL of the additional portion was distilled off again by concentration under reduced pressure, the residual free acid concentration decreased to 6000 ppm by mass.

[Example 1-13]
As a result of carrying out the reaction in the same procedure as in Example 1-1 except that the fluorinating agent was changed to acidic potassium fluoride (15.5 g, 198.7 mmol, 2.0 equivalents), difluoroionic complex (2a- The conversion rate to Li) is 13.6%, the selectivity is 94.4%, and the residual chlorine concentration and the residual free acid concentration are less than 100 ppm by mass, respectively, based on the difluoroionic complex (2a-Li). It was 5000 mass ppm.

[Example 1-14]
As a result of carrying out the reaction in the same procedure as in Example 1-1 except that the fluorinating agent was changed to acidic potassium fluoride (46.6 g, 596.2 mmol, 6.0 equivalents), a difluoroionic complex (2a- The conversion to Li) is 29.5, the selectivity is 87.5%, and the residual chlorine concentration and the residual free acid concentration are less than 100 ppm by mass, respectively, based on the difluoroionic complex (2a-Li), and 10,000 The mass was ppm.

The contents of the above Examples 1-1 to 1-14 are shown in the following Table 1 (conditions) and Table 2 (results). In Table 1, the tricoordinator (1) is a hexacoordinate ionic complex (1) in which three molecules of a bidentate ligand are coordinated, Et ₃ N · 3HF is triethylamine hydrogen trifluoride, KF -HF represents acidic potassium fluoride. Incidentally, “4000 → 2000” or the like in the free acid concentration means that the removal under reduced pressure was performed again to reduce the free acid concentration.

  The above results are summarized. When the molar equivalent of the fluorinating agent HF is 1.8 or 2.0 and the temperature is 25 ° C., the formation of the target product (2a-Li) can be confirmed after 24 hours, but the conversion rate is 25.0 to 29. 6% (Examples 1-1 and 1-2). On the other hand, when extended to 72 hours at 2.0 molar equivalents of HF and a temperature of 25 ° C., the conversion rate to (2a-Li) was improved to 37.7% (Example 1-3). ). As a result of further increasing the temperature to 40 ° C., the conversion rate was improved to 50.5% (Example 1-4). When the temperature was raised to 80 ° C. for 24 hours, the conversion rate was about 51.3%. (Example 1-5)

  As described above, the conversion rate increased only to about 50% at HF 1.8 to 2.0 molar equivalents. Therefore, the reaction was carried out by increasing the molar equivalent of HF. At HF 6.0 and 10.0 molar equivalents, at temperatures of 25 ° C. and 24 hours, the conversion rates were significantly improved to 71.0% and 92.3%, respectively (Examples 1-6, 1- 8). Even at HF 6.0 molar equivalent and a temperature of 25 ° C., the conversion rate was increased to 90.0%, which was the same as 10.0 molar equivalent of HF, by extending to 48 hours (Example 1-7). Further, as the molar equivalent of HF was increased, the reaction rate was improved, with a conversion rate of 93.4% (Example 1-9) in 3 hours for HF 20.0 molar equivalents, and conversion in 1 hour for HF 40.0 molar equivalents. The rate was 91.0% (Example 1-10).

  As a result of fluorination by changing the fluorinating agent used from HF to triethylamine trifluoride, the formation of the target product (2a-Li) can be confirmed, but the conversion rate and selectivity compared to HF Decrease was observed. It seems that the production of phosphoric acid fluoride other than the target product progressed under the influence of triethylamine (Examples 1-11 and 1-12).

  As a result of fluorination by changing the fluorinating agent to be used from HF to acidic potassium fluoride, the formation of the target product (2a-Li) can be confirmed, but the conversion rate is lower than that of HF. It was. (Examples 1-13 and 1-14). From this, it is considered that the potassium fluoride component in the acidic potassium fluoride has a low effect of accelerating the reaction.

  In Examples 1-1 to 1-14, since chlorides were not included in the raw material, the residual chlorine concentration was less than 100 ppm by mass. In Examples 1-9 and 1-10, in which the amount of HF added was particularly large, the residual free acid concentration increased, and the removal under reduced pressure was performed again. In the system using triethylamine hydrogen trifluoride, the amount of residual free acid was larger than that in the system using only HF.

[Example 2-1]
According to the method disclosed in Non-Patent Document 2, lithium trisoxalatophosphate (1a-Li), which is a hexacoordinate ionic complex in which three molecules of oxalic acid are coordinated, was obtained. This (1a-Li) (30 g, 99.4 mmol) was dissolved in EMC (120 mL), HF (4.0 g, 198.7 mmol, 2.0 molar equivalents) was added, and then an acid was added to accelerate the reaction. Hydrogen chloride (hereinafter HCl) (7.3 g, 198.7 mmol, 2.0 molar equivalents) was added. After stirring at 25 ° C. for 3 hours, the remaining HF and the added acid were removed and concentrated under reduced pressure. After removing the precipitated oxalic acid by filtration, the conversion rate and selectivity were determined by F, P-NMR, the residual chlorine concentration by silver nitrate titration, and the residual free acid concentration by free acid titration. The conversion rate to a difluoroionic complex (2a-Li) in which two molecules of oxalic acid are coordinated is 42.6% and the selectivity is 80.4%. The residual chlorine concentration and the residual free acid concentration are difluoroions. The amount was less than 100 ppm by mass and 2000 ppm by mass based on the sex complex (2a-Li), respectively.

[Example 2-2]
As a result of carrying out the reaction in the same procedure as in Example 2-1, except that the reaction time was changed from 3 hours to 24 hours, the conversion rate to the difluoroionic complex (2a-Li) was 72.8%, and the selectivity The residual chlorine concentration and the residual free acid concentration were respectively less than 100 ppm by mass and 2000 ppm by mass based on the difluoroionic complex (2a-Li).

[Example 2-3]
The same procedure as Example 2-1 except that the acid was changed from HCl to trifluoromethanesulfonic acid (hereinafter TfOH) (0.3 g, 2.0 mmol, 0.02 molar equivalent), and the reaction time was changed from 3 hours to 6 hours. As a result, the conversion rate to the difluoroionic complex (2a-Li) was 93.2% and the selectivity was 94.1%. The residual chlorine concentration and the residual free acid concentration were difluoroionic. They were less than 100 ppm by mass and 2500 ppm by mass, respectively, based on the complex (2a-Li).

[Example 2-4]
Example 2-1 except that the acid was changed from HCl to TfOH (0.3 g, 2.0 mmol, 0.02 molar equivalent), the reaction time was changed from 3 hours to 24 hours, and the reaction temperature was changed from 25 ° C. to 0 ° C. As a result of performing the reaction in the same procedure as above, the conversion rate to the difluoroionic complex (2a-Li) is 94.2%, the selectivity is 95.2%, the residual chlorine concentration and the residual free acid concentration are They were less than 100 ppm by mass and 2500 ppm by mass, respectively, based on the difluoroionic complex (2a-Li).

[Example 2-5]
Example 2-1 except that the acid was changed from HCl to TfOH (0.3 g, 2.0 mmol, 0.02 molar equivalent), the reaction time was changed from 3 hours to 1 hour, and the reaction temperature was changed from 25 ° C. to 40 ° C. As a result of performing the reaction in the same procedure, the conversion rate to the difluoroionic complex (2a-Li) was 91.2%, the selectivity was 92.0%, the residual chlorine concentration and the residual free acid concentration were They were less than 100 ppm by mass and 2500 ppm by mass, respectively, based on the difluoroionic complex (2a-Li).

[Example 2-6]
Results obtained by performing the reaction in the same procedure as in Example 2-1, except that the acid was changed from HCl to TfOH (0.03 g, 0.2 mmol, 0.002 molar equivalent), and the reaction time was changed from 3 hours to 72 hours. The conversion rate to the difluoroionic complex (2a-Li) is 95.2%, the selectivity is 96.0%, and the residual chlorine concentration and the residual free acid concentration are the same as those of the difluoroionic complex (2a-Li). The standards were less than 100 mass ppm and 2000 mass ppm, respectively.

[Example 2-7]
As a result of carrying out the reaction in the same procedure as in Example 2-2 except that the acid was changed from HCl to trifluoroacetic acid (hereinafter TFA) (0.1 g, 1.0 mmol, 0.01 molar equivalent), difluoroionic properties were obtained. The conversion rate to the complex (2a-Li) was 35.6% and the selectivity was 97.0%. The residual chlorine concentration and the residual free acid concentration were 100 based on the difluoroionic complex (2a-Li), respectively. It was less than mass ppm and 2000 mass ppm.

[Example 2-8]
As a result of carrying out the reaction in the same procedure as in Example 2-2 except that the acid was changed from HCl to TFA (1.1 g, 9.9 mmol, 0.1 molar equivalent), the difluoroionic complex (2a-Li) The conversion rate to 53.2% and the selectivity are 96.6%, and the residual chlorine concentration and the residual free acid concentration are less than 100 ppm by mass, respectively, and 2500 masses based on the difluoroionic complex (2a-Li). ppm.

[Example 2-9]
Fluorinating agent from HF to lithium fluoride (hereinafter LiF) (5.2 g, 198.7 mmol, 2.0 molar equivalent), acid from HCl to TfOH (29.8 g, 198.7 mmol, 2.0 molar equivalent) As a result of carrying out the reaction in the same procedure as in Example 2-2, except that it was changed to 2, the conversion rate to the difluoroionic complex (2a-Li) was 30.2%, and the selectivity was 95.2%. The residual chlorine concentration and the residual free acid concentration were less than 100 ppm by mass and 4000 ppm by mass, respectively, based on the difluoroionic complex (2a-Li).

[Example 2-10]
Fluorinating agent from HF to sodium fluoride (hereinafter NaF) (8.3 g, 198.7 mmol, 2.0 molar equivalent), acid from HCl to TfOH (29.8 g, 198.7 mmol, 2.0 molar equivalent) As a result of carrying out the reaction in the same procedure as in Example 2-2, except that it was changed to 3, the conversion rate to the difluoroionic complex (2a-Li) was 30.9%, and the selectivity was 94.3%. The residual chlorine concentration and the residual free acid concentration were less than 100 ppm by mass and 4000 ppm by mass, respectively, based on the difluoroionic complex (2a-Li).

[Example 2-11]
Fluorinating agent from HF to potassium fluoride (hereinafter KF) (11.5 g, 198.7 mmol, 2.0 molar equivalent); acid from HCl to TfOH (29.8 g, 198.7 mmol, 2.0 molar equivalent) As a result of carrying out the reaction in the same procedure as in Example 2-2, except that it was changed to 2, the conversion rate to the difluoroionic complex (2a-Li) was 32.1%, and the selectivity was 94.8%. The residual chlorine concentration and the residual free acid concentration were less than 100 ppm by mass and 4000 ppm by mass, respectively, based on the difluoroionic complex (2a-Li).

[Example 2-12]
Example 2 except that the acid was changed from HCl to TfOH (0.03 g, 0.2 mmol, 0.002 molar equivalent), the reaction time was changed from 3 hours to 72 hours, and the solvent was changed from EMC to dimethyl carbonate (hereinafter DMC). As a result of performing the reaction in the same procedure as -1, the conversion rate to the difluoroionic complex (2a-Li) was 94.9%, the selectivity was 95.7%, and the residual chlorine concentration and residual free acid concentration Were less than 100 ppm by mass and 2000 ppm by mass, respectively, based on the difluoroionic complex (2a-Li).

[Example 2-13]
Example 2 except that the acid was changed from HCl to TfOH (0.03 g, 0.2 mmol, 0.002 molar equivalent), the reaction time was changed from 3 hours to 72 hours, and the solvent was changed from EMC to diethyl carbonate (hereinafter DEC). As a result of carrying out the reaction in the same procedure as -1, the conversion rate to the difluoroionic complex (2a-Li) was 93.5%, the selectivity was 94.6%, and the residual chlorine concentration and residual free acid concentration Were less than 100 ppm by mass and 2500 ppm by mass, respectively, based on the difluoroionic complex (2a-Li).

[Example 2-14]
Example 2 except that the acid was changed from HCl to TfOH (0.03 g, 0.2 mmol, 0.002 molar equivalent), the reaction time was changed from 3 hours to 72 hours, and the solvent was changed from EMC to tetrahydrofuran (hereinafter THF). As a result of performing the reaction in the same procedure as 1, the conversion rate to the difluoroionic complex (2a-Li) was 92.2%, the selectivity was 93.9%, and the residual chlorine concentration and the residual free acid concentration were And less than 100 ppm by mass and 2000 ppm by mass, respectively, based on the difluoroionic complex (2a-Li).

[Example 2-15]
Example 2 except that the acid was changed from HCl to TfOH (0.03 g, 0.2 mmol, 0.002 molar equivalent), the reaction time was changed from 3 hours to 72 hours, and the solvent was changed from EMC to ethyl acetate (hereinafter AcOEt). As a result of performing the reaction in the same procedure as -1, the conversion rate to the difluoroionic complex (2a-Li) was 91.1%, the selectivity was 92.2%, the residual chlorine concentration and the residual free acid concentration Were less than 100 ppm by mass and 2000 ppm by mass, respectively, based on the difluoroionic complex (2a-Li).

[Example 2-16]
Example except that the acid was changed from HCl to TfOH (0.03 g, 0.2 mmol, 0.002 molar equivalent), the reaction time was changed from 3 hours to 72 hours, and the solvent was changed from EMC to acetonitrile (hereinafter CH ₃ CN). As a result of carrying out the reaction in the same procedure as in 2-1, the conversion rate to the difluoroionic complex (2a-Li) was 90.5%, the selectivity was 92.3%, the residual chlorine concentration and the residual free acid The concentrations were less than 100 ppm by mass and 3000 ppm by mass, respectively, based on the difluoroionic complex (2a-Li).

[Example 2-17]
According to the method disclosed in Non-Patent Document 2, lithium trisoxalatophosphate (1a-Li), which is a hexacoordinate ionic complex in which three molecules of oxalic acid are coordinated, was obtained. 500 g of strongly acidic cation exchange resin 252 (hereinafter referred to as “ion exchange resin”) manufactured by Dow Chemical was weighed and immersed in a 0.1 N aqueous sodium hydroxide solution (2.5 kg), and stirred at 25 ° C. for 6 hours. The ion exchange resin was collected by filtration and washed thoroughly with pure water until the pH of the washing solution was 8 or less. Thereafter, moisture was removed by drying under reduced pressure (120 ° C., 1.3 kPa) for 12 hours. (1a-Li) (30 g, 99.4 mmol) was dissolved in EMC (270 mL), 150 g of the dried ion exchange resin was added thereto, and the mixture was stirred at 25 ° C. for 6 hours. Then, by removing the ion exchange resin by filtration, a (1a-Na) / EMC solution in which cations were exchanged from Li ⁺ to Na ⁺ was obtained. When the cation was quantified by ion chromatography, the ratio of Na ⁺ / Li ⁺ was 99.5.
Concentration under reduced pressure was performed until the salt concentration of the (1a-Na) / EMC solution was about 20% by mass. Then HF (4.0 g, 198.7 mmol, 2.0 molar equivalent) and TfOH (0.03 g, 0.2 mmol, 0.002 molar equivalent) were added. After stirring at a temperature of 25 ° C. for 72 hours, residual HF and the added acid were removed and concentrated under reduced pressure. After removing the precipitated oxalic acid by filtration, the conversion rate and selectivity were determined by F, P-NMR, the residual chlorine concentration by silver nitrate titration, and the residual free acid concentration by free acid titration. The conversion rate to the difluoroionic complex (2a-Na) is 94.8%, the selectivity is 96.0%, and the residual chlorine concentration and the residual free acid concentration are the same as the difluoroionic complex (2a-Na). The standards were less than 100 mass ppm and 2000 mass ppm, respectively.

[Example 2-18]
According to the method disclosed in Non-Patent Document 2, lithium trisoxalatophosphate (1a-Li), which is a hexacoordinate ionic complex in which three molecules of oxalic acid are coordinated, was obtained. This (1a-Li) (30 g, 99.4 mmol) was dissolved in EMC (150 mL), trimethylpropylammonium chloride (14.4 g, 104.4 mmol) was added thereto, and the mixture was stirred at 45 ° C. for 6 hours. . After cooling to 5 ° C., insoluble matters were removed by filtration to obtain a (1a-TMPA) / EMC solution in which cations were exchanged from Li ⁺ to trimethylpropylammonium cation (hereinafter referred to as TMPA). When the cation was quantified by ion chromatography, the ratio of TMPA / Li ⁺ was 98.4.
HF (4.0 g, 198.7 mmol, 2.0 molar equivalent) and TfOH (0.03 g, 0.2 mmol, 0.002 molar equivalent) were added to the (1a-TMPA) / EMC solution. After stirring at a temperature of 25 ° C. for 72 hours, residual HF and the added acid were removed and concentrated under reduced pressure. After removing the precipitated oxalic acid by filtration, the conversion rate and selectivity were determined by F, P-NMR, the residual chlorine concentration by silver nitrate titration, and the residual free acid concentration by free acid titration. The conversion rate to the difluoroionic complex (2a-TMPA) is 90.1%, the selectivity is 93.5%, and the residual chlorine concentration and residual free acid concentration are the same as the difluoroionic complex (2a-TMPA). The reference values were 200 ppm by mass and 2000 ppm by mass, respectively.

[Example 2-19]
Referring to the method disclosed in Non-Patent Document 2, lithium tris (hexafluoro-2-hydroxyisobutyrate), which is a hexacoordinate ionic complex in which three molecules of hexafluoro-2-hydroxyisobutyric acid are coordinated (1b-Li) was obtained. This (1b-Li) (66.4 g, 99.4 mmol) was dissolved in EMC (150 mL), HF (4.0 g, 198.7 mmol, 2.0 molar equivalents) and TfOH (0.03 g, 0.0. 2 mmol, 0.002 molar equivalent) was added. After stirring at a temperature of 25 ° C. for 72 hours, the remaining HF, hexafluoro-2-hydroxyisobutyric acid and the added acid were removed and concentrated under reduced pressure. After the precipitated solid was removed by filtration, the conversion rate and selectivity were determined by F and P-NMR, the residual chlorine concentration was determined by silver nitrate titration, and the residual free acid concentration was determined by free acid titration. Conversion to difluoroionic complex (2b-Li) in which two molecules of hexafluoro-2-hydroxyisobutyric acid are coordinated is 92.1%, and selectivity is 94.5%. Residual chlorine concentration and residual free acid The concentrations were less than 100 ppm by mass and 20000 ppm by mass, respectively, based on the difluoroionic complex (2b-Li).

[Example 2-20]
Referring to the method disclosed in Non-Patent Document 2, tris (tetratrifluoromethylethanediolato) lithium phosphate (1c-Li), which is a hexacoordinate ionic complex in which three molecules of perfluoropinacol are coordinated, is obtained. It was. This (1c-Li) (102.7 g, 99.4 mmol) was dissolved in EMC (200 mL), and HF (4.0 g, 198.7 mmol, 2.0 molar equivalents) and TfOH (0.03 g, 0.0. 2 mmol, 0.002 molar equivalent) was added. After stirring at a temperature of 25 ° C. for 72 hours, the remaining HF, perfluoropinacol and the added acid were removed and concentrated under reduced pressure. After the precipitated solid was removed by filtration, the conversion rate and selectivity were determined by F and P-NMR, the residual chlorine concentration was determined by silver nitrate titration, and the residual free acid concentration was determined by free acid titration. The conversion rate to a difluoroionic complex (2c-Li) in which two molecules of perfluoropinacol are coordinated is 90.5%, and the selectivity is 91.6%. The residual chlorine concentration and the residual free acid concentration are difluoro ions. Was less than 100 ppm by mass and 10000 ppm by mass, respectively, based on the sex complex (2c-Li).

  The contents of the above Examples 2-1 to 2-20 are shown in Table 3 (conditions) and Table 4 (results) below. In Table 3, HHIB represents hexafluoro-2-hydroxyisobutyric acid, and PFP represents perfluoropinacol.

  The above results are summarized. It has been clarified that the fluorination of the trimolecular coordination body (1a-Li) proceeds at a high conversion rate by using HF excessively. Since it can be presumed that the proton concentration in the reaction solution increased due to excess HF, and thereby the reaction rate was improved, addition of an acid having a higher degree of dissociation was attempted. When fluorination reaction was carried out by adding 2.0 molar equivalents of HCl in addition to 2.0 molar equivalents of HF, the conversion rate was 42.6% at 25 ° C. for 3 hours and 72.8% at 24 hours (Examples). 2-1, 2-2). It can be seen that the reaction rate was significantly improved as compared with the result of Example 1-2 in which no HCl was used. However, since the selectivity decreased due to the side reaction caused by HCl, the search for a more effective acid was performed.

  As a result of performing fluorination by replacing the acid with TfOH, a very high addition effect was observed even at 0.02 molar equivalent, conversion rate 93.2% (Example 2-3) at 25 ° C. for 6 hours, 40 ° C. for 1 hour. The conversion rate was 91.2% (Example 2-5), and the conversion rate was 94.2% (Example 2-4) by extending it to 24 hours even at 0 ° C. Further, even at a TfOH 0.002 molar equivalent in which the amount added was reduced, the conversion rate could be improved to 95.2% without decreasing the selectivity by extending the time to 72 hours (Example 2-). 6).

  Next, as a result of fluorination by replacing the acid with TFA, the conversion rate was 35.6% (Example 2-7) at 0.01 molar equivalents at 25 ° C. for 24 hours, and conversion at 0.1 molar equivalents. The rate was 53.2% (Example 2-8), and although an improvement was seen as compared with the case without TFA, the effect of TfOH was not obtained.

  The fluorinating agent was changed to a metal fluorinated product (LiF, NaF, KF), and the fluorination reaction was performed in the presence of TfOH. As a result, the target product (2a-Li) was obtained with a conversion rate of about 30%. (Examples 2-9, 2-10, 2-11) This is a slight improvement from the results of Example 1-2 in which only 2.0 molar equivalents of HF were used without using TfOH. . The metal fluoride is protonated by TfOH, and 2.0 molar equivalents of HF are generated in the system, and it is considered that fluorination has progressed. However, trifluoromethanesulfonate exhibits the Lewis acid effect. As a result, the conversion rate is likely to be improved.

The fluorination reaction was carried out by changing the solvent from EMC under the conditions of HF 2.0 molar equivalent, TfOH 0.002 molar equivalent, and 25 ° C. for 72 hours. As a result, the conversion rate was the same as that of EMC for DMC and DEC (Examples 2-12 and 2-13), and was slightly decreased for THF, AcOEt and CH ₃ CN (Examples 2-14 and 2). -15 and 2-16), but the conversion rate was 90% or more.

Using cation of Li ⁺ changed from Li ⁺ to Na ⁺ (1a-Na) or TMPA (1a-TMPA), HF 2.0 molar equivalent, TfOH 0.002 molar equivalent, 25 ° C. for 72 hours As a result of the fluorination, the reaction proceeded without any problem. (2a-Na) had a conversion rate of 94.8% (Example 2-17) and (2a-TMPA) had a conversion rate of 90.1% (implementation). Obtained in Example 2-18).

  The raw material ligand was changed from oxalic acid to HHIB (1b-Li) or PFP (1c-Li), HF 2.0 molar equivalent, TfOH 0.002 molar equivalent, 25 ° C. for 72 hours. As a result of fluorination under the conditions, the reaction proceeded without any problem. (2b-Li) was 92.1% conversion (Example 2-19) and (2c-Li) was 90.5% conversion ( Obtained in Example 2-20).

As described above, it has been clarified that the addition of an acid significantly improves the HF fluorination rate. Further, even when the cation was changed from Li ⁺ to Na ⁺ or TMPA and the ligand was changed from oxalic acid to HHIB or PFP, the target difluoroionic complex could be obtained efficiently.

  Residual chlorine concentration was less than 100 mass ppm except for Example 2-18. The residual chlorine concentration of Example 2-18 is 200 ppm by mass, which seems to be brought from the chloride used when synthesizing the trimolecular coordination body (1a-TMPA) as a raw material. It is.

When the ligand was oxalic acid, the residual free acid concentration increased up to 4000 mass ppm in the systems with a large amount of acid added (Examples 2-9, 2-10, 2-11). The solvent was 2000 to 2500 mass ppm except that the solvent was 3000 mass ppm in the CH ₃ CN system (Example 2-16). When the ligand was HHIB, the residual free acid concentration was as extremely high as 20000 mass ppm. This is because the high solubility of HHIB could not be removed sufficiently by concentration and filtration operations. Similarly, in the case of PFP having high solubility, the residual free acid concentration was as high as 10,000 ppm by mass. Since PFP has higher volatility than HHIB, it is considered that it was partially distilled off during concentration.

[Comparative Example 1-1]
The reaction was carried out with reference to the method described in Patent Document 10. LiPF ₆ (20.0 g, 132.0 mmol), 110 mL of EMC, and oxalic acid (11.9 g, 132.0 mmol) were added to a 500 mL glass flask. At this time, LiPF ₆ was completely dissolved, but most of oxalic acid remained undissolved. Under stirring at 40 ° C., silicon tetrachloride (13.4 g, 79 mmol) was dropped into the flask over 1.5 hours, and then stirring was continued for 2.5 hours. Subsequently, tetrafluorosilane and hydrochloric acid were removed under reduced pressure, and the insoluble matter was removed by filtration to obtain a difluoroionic complex (2a-Li). Conversion to difluoroionic complex (2a-Li) is 92.5%, selectivity is 92.5%. Residual chlorine concentration and residual free acid concentration are based on difluoroionic complex (2a-Li). As 1500 ppm by mass and 2000 ppm by mass, respectively.

[Comparative Example 1-2]
As a result of carrying out the reaction in the same procedure as in Example 1-1 except that the fluorinating agent was changed from HF to lithium fluoride (hereinafter LiF) (5.2 g, 198.7 mmol, 2.0 molar equivalent), difluoro Formation of the ionic complex (2a-Li) could not be confirmed.

[Comparative Example 1-3]
As a result of carrying out the reaction in the same procedure as in Example 1-1, except that the fluorinating agent was changed from HF to sodium fluoride (hereinafter NaF) (8.3 g, 198.7 mmol, 2.0 molar equivalent), difluoro Formation of the ionic complex (2a-Li) could not be confirmed.

[Comparative Example 1-4]
As a result of carrying out the reaction in the same procedure as Example 1-1, except that the fluorinating agent was changed from HF to potassium fluoride (hereinafter KF) (11.5 g, 198.7 mmol, 2.0 molar equivalent), difluoro Formation of the ionic complex (2a-Li) could not be confirmed.

[Comparative Example 1-5]
As a result of carrying out the reaction in the same procedure as in Example 1-1, except that the fluorinating agent was changed from HF to a tetrabutylammonium fluoride / THF solution (199 mL, 2.0 molar equivalent) at a concentration of 1 mol / L. Formation of the ionic complex (2a-Li) could not be confirmed.

[Comparative Example 1-6]
As a result of carrying out the reaction in the same procedure as in Example 1-1, except that the fluorinating agent was changed from HF to triethylamine hydrofluoride (24.1 g, 198.7 mmol, 2.0 molar equivalent), difluoroionic properties were obtained. Formation of the complex (2a-Li) could not be confirmed.

The contents of the above Comparative Examples 1-1 to 1-6 are shown in Table 5 (Condition) and Table 6 (Result) below. In Table 5, TBAF represents tetrabutylammonium fluoride, and Et ₃ N · 3HF represents triethylamine trifluoride.

 In Comparative Examples 1-2 to 1-6, fluorination was attempted under non-acidic conditions, but in any case, the formation of the target product (2a-Li) could not be confirmed, and fluorination of the trimolecular coordination body was not possible. Obviously, it needs the help of a protonic acid or a Lewis acid. Comparative Example 1-1 was carried out by the method disclosed in Patent Document 10, but the conversion rate and selectivity were slightly from the results of fluorination of the trimolecular coordination body (Example 2-6). In addition, the chlorine concentration was significantly increased to 1500 mass ppm.

Claims (13)

A six-coordinated ionic complex (1) represented by the general formula (1) in a non-aqueous solvent , acidic potassium fluoride, acidic sodium fluoride, acidic ammonium fluoride, hydrogen fluoride-excess organic amine hydrofluoride, A method for producing a difluoroionic complex (2) represented by the general formula (2), wherein the fluorination is performed with one or more fluorinating agents selected from the group consisting of hydrogen fluoride .


In the general formulas (1) and (2), A ⁺ is any one selected from the group consisting of metal ions, protons and onium ions, and M is any one selected from the group consisting of P, As and Sb. One. F is a fluorine atom. O is an oxygen atom.
Y is a carbon atom or a sulfur atom. Q is 1 when Y is a carbon atom. Q is 1 or 2 when Y is a sulfur atom.
W is a hydrocarbon group that may have a heteroatom having 1 to 10 carbon atoms and / or a halogen atom (in the case where the number of carbon atoms is 3 or more, a branched chain or cyclic structure can also be used), Or -N (R < ¹ >)-is represented. In this case, R ¹ represents a hydrogen atom, an alkali metal, hydrocarbon group which may have a hetero atom and / or a halogen atom having 1 to 10 carbon atoms. When the number of carbon atoms is 3 or more, R ¹ can take a branched chain or a cyclic structure. Z is a carbon atom. p is 0 or 1, q is an integer of 0 to 2, r is an integer of 0 to 2, s represents 0 or 1, and p + r ≧ 1. However, when s is 0, there is no oxygen atom double-bonded to Z. A six-coordinated ionic complex (1) represented by the general formula (1) in a non-aqueous solvent , acidic potassium fluoride, acidic sodium fluoride, acidic ammonium fluoride, hydrogen fluoride-excess organic amine hydrofluoride, Hydrogen fluoride, potassium fluoride, sodium fluoride, lithium fluoride, cesium fluoride, nickel fluoride, calcium fluoride, antimony fluoride, iron fluoride, zinc fluoride, manganese fluoride, ytterbium fluoride, fluoride A method of fluorinating with one or more fluorinating agents selected from the group consisting of hafnium, cobalt fluoride, ammonium fluoride, and tetrabutylammonium fluoride . During fluorination, sulfuric acid, fluorosulfuric acid, hydrogen chloride, methane Sulfonic acid, trifluoromethanesulfonic acid, trifluoroacetic acid, nitric acid, p-toluenesulfonic acid, trifluoride One or more acids or Lewis acids selected from the group consisting of boron, phosphorus pentafluoride, aluminum trichloride, niobium pentachloride, and metal trifluoromethanesulfonate are added to a non-aqueous solvent. A method for producing the difluoroionic complex (2) represented by (2).


In the general formulas (1) and (2), A ⁺ is any one selected from the group consisting of metal ions, protons and onium ions, and M is any one selected from the group consisting of P, As and Sb. One. F is a fluorine atom. O is an oxygen atom.
Y is a carbon atom or a sulfur atom. Q is 1 when Y is a carbon atom. Q is 1 or 2 when Y is a sulfur atom.
W is a hydrocarbon group that may have a heteroatom having 1 to 10 carbon atoms and / or a halogen atom (in the case where the number of carbon atoms is 3 or more, a branched chain or cyclic structure can also be used), Or -N (R < ¹ >)-is represented. In this case, R ¹ represents a hydrogen atom, an alkali metal, hydrocarbon group which may have a hetero atom and / or a halogen atom having 1 to 10 carbon atoms. When the number of carbon atoms is 3 or more, R ¹ can take a branched chain or a cyclic structure. Z is a carbon atom. p is 0 or 1, q is an integer of 0 to 2, r is an integer of 0 to 2, s represents 0 or 1, and p + r ≧ 1. However, when s is 0, there is no oxygen atom double-bonded to Z. Each element of the hexacoordinate ionic complex (1) and the difluoroionic complex (2) is at least one combination selected from the following (a), (b), and (c) The manufacturing method of Claim 1 or 2 .
(A) M = P, Y = C, p, q, s = 1, r = 0
(B) M = P, W = C (CF ₃ ) ₂ , p, q = 0, r, s = 1
(C) M = P, W = C (CF ₃ ) ₂ , p, q, s = 0, r = 2 The manufacturing method according to any one of claims 1 to 3 , wherein the equivalent of the fluorinating agent is 1.5 to 50 molar equivalents relative to the hexacoordinate ionic complex (1). . The fluorinating agent comprises hydrogen fluoride;
2. The production method according to claim 1, wherein the equivalent of hydrogen fluoride as the fluorinating agent is 1.5 to 50 molar equivalents relative to the six-coordinated ionic complex (1). The production method according to claim 2 , wherein an equivalent amount of the acid or Lewis acid is 0.001 to 2.0 molar equivalents relative to the hexacoordinate ionic complex (1). The acid is one or more selected from the group consisting of trifluoromethanesulfonic acid, methanesulfonic acid, and trifluoroacetic acid, and the equivalent of an acid other than the fluorinating agent is based on the six-coordinated ionic complex (1). It is 0.001-2.0 molar equivalent, The manufacturing method of Claim 2 characterized by the above-mentioned. The fluorinating agent is hydrogen fluoride, claim, wherein the acid other than said fluorinated agent is trifluoromethanesulfonic acid, methanesulfonic acid, one or more members selected from the group consisting of trifluoroacetic acid 2 The manufacturing method as described in. The non-aqueous solvent is one selected from the group consisting of carbonates, esters, ketones, lactones, ethers, nitriles, amides and sulfones, or a mixture thereof. Item 9. The production method according to any one of Items 1 to 8 . The nonaqueous solvent is dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, butyl propionate, acetone, ethyl methyl ketone, Diethyl ketone, γ-butyrolactone, γ-valerolactone, tetrahydrofuran, tetrahydropyran, dibutyl ether, diisopropyl ether, 1,2-dimethoxyethane, 1,2-diethoxyethane, acetonitrile, propionitrile, N, N-dimethylformamide , one selected from the group consisting of dimethyl sulfoxide, sulfolane, or process according to any one of claims 1 to 9, characterized in that a mixture thereof. The production method according to any one of claims 1 to 10 , wherein the fluorination is carried out at a temperature of -60 ° C to 150 ° C. The production method according to any one of claims 1 to 11 , wherein a pressure reduction operation is performed after fluorination. The ligand of the six-coordinated ionic complex (1) and the difluoroionic complex (2) is oxalic acid, and the oxalic acid deposited by the depressurization operation after fluorination is separated by filtration. The manufacturing method according to any one of claims 1 to 12 .