JP5227524B2 - Ionic liquid having sulfonium cation containing SN bond and method for producing the same - Google Patents

Description

  The present invention relates to an ionic liquid that exhibits a liquid state in a wide temperature range and is excellent in electrochemical stability, and a method for producing the same, and a power storage device, a lithium secondary battery, an electric double layer capacitor, a dye-sensitized type using the ionic liquid The present invention relates to various uses such as solar cells, fuel cells, and reaction solvents.

Many ionic liquids formed as cations having a relatively low viscosity and melting point, such as imidazolium, have been reported. However, these ionic liquids often have drawbacks such as low reduction stability, lack of stability due to a narrow potential window, and difficulty in adapting to electrolytes for power storage devices. Furthermore, some ionic liquids with relatively low melting points may have low thermal decomposition temperatures and lack stability. (See Patent Document 1, Non-Patent Documents 1 and 2)
As an ionic liquid that is stable in a wide temperature range, an ionic liquid formed using an onium containing an N atom as represented by an ammonium cation as a cation has been reported. However, an ionic liquid having an ammonium-based cation has a relatively high melting point and viscosity, and only a part of the structure becomes a liquid having a low viscosity near room temperature. (See Patent Document 2, Patent Document 3, and Non-Patent Documents 3 to 6)

  In other words, a lithium secondary battery, an electric double layer capacitor, a fuel cell or a dye-sensitized solar cell, or an electric storage battery has a stable liquid state in a wide temperature range and a small amount of ionic liquid excellent in electrochemical stability. This is a major obstacle for applications as electrolytes, electrolytes or additives for industrial devices.

JP-T-2001-517205 International Publication No. 02/076924 Pamphlet JP 2003-331918 A Kaji principle, Electrochemistry, 70, No.2, 130 (2002) Y. Katayama, S. Dan, T. Miura and T. Kishi, Journal of The Electrochemical Society, 148 (2), C102-C105 (2001) Matsumoto Hajime, Miyazaki Yoshinori, Molten salt and high temperature chemistry, 44, 7 (2001) H. Matsumoto, M. Yanagida, K. Tanimoto, M. Nomura, Y. Kitagawa and Y. Miyazaki, Chem. Lett, 8, 922 (2000) D.R.MacFarlane, J.Sun, J. Golding, P. Meakin and M. Forsyth, Electrochemica Acta, 45, 1271 (2000) Doulas R. MacFarlane, Jake Golding, Stewart Forsyth, Maria Forsyth and Glen B. Deacon, Chem. Commun., 1430 (2001)

  An object of the present invention is to provide an ionic liquid which exhibits a stable liquid state in a wide temperature range and is excellent in electrochemical stability, and a method for producing the ionic liquid. It is intended to provide an ionic liquid that can be used as a material used for an electric double layer capacitor, a dye-sensitized solar cell, a fuel cell, a reaction solvent, etc. The object is to provide an ionic liquid containing a novel sulfonium cation.

  As a result of synthesizing a large number of salts composed of a cation component and an anion component and intensively studying an ionic liquid for achieving the above object, the present inventors have found that a sulfonium ion containing at least one S—N bond, particularly An ionic liquid containing one or more kinds of components selected from the group of organic cations represented by the formula (1) as a cation component can form an ionic liquid that is stable in a wide temperature range and excellent in electrochemical stability. I found out.

[式中の置換基Ｒ¹〜Ｒ⁸は互いに独立していて、同一であっても異なっていても良い。置換基Ｒ¹〜Ｒ⁸はそれぞれ、Ｈ原子、Ｃ₁〜Ｃ₃₀の直鎖状または側鎖を有するアルキル基、Ｃ₂〜Ｃ₃₀の単一もしくは複数の二重結合を持つ直鎖状または側鎖を有するアルケニル基、Ｃ₂〜Ｃ₃₀の単一もしくは複数の三重結合を持つ直鎖状または側鎖を有するアルキニル基、飽和または部分的にもしくは完全に不飽和のシクロアルキル基、アリール基、複素環基のいずれかを示す。また、これらの置換基Ｒ¹〜Ｒ⁸のうちの単一または複数の置換基に含まれるＨ原子は、ハロゲン原子によって部分的にもしくは完全に置換でき、あるいは、ＣＮ基、ＮＯ₂基によって部分的に置換できる。また、置換基Ｒ¹〜Ｒ⁸のうちの任意の置換基が共同で環状構造を形成していてもよい。また、これらの置換基Ｒ¹〜Ｒ⁸に含まれる炭素原子は、-O-,-Si(R')₂-,-C(O)-,-C(O)O-,-S-,-S(O)-,-SO₂-,-SO₃-,-N=,-N=N-,-NH-,-NR'-,-PR'-,-P(O)R'-,-P(O)R'-O-,-O-P(O)R'-O-,および-P(R')₂=N-の群から選択した原子および／または原子団によって置換できる（ここで、R'はＣ₁〜Ｃ₁₀の直鎖状または側鎖を有するアルキル基、またはＦ原子によって部分的もしくは完全に置換されたアルキル基、飽和または部分的にもしくは完全に不飽和のシクロアルキル基、非置換もしくは置換されたフェニル基、または非置換もしくは置換されたヘテロシクルスを示す）。Ｘ¹およびＸ²は互いに独立して、Ｎ原子、Ｏ原子、またはＣ原子を示す。また、Ｒ⁴、Ｒ⁷は、Ｘ¹またはＸ²がＮ原子またはＣ原子の場合のみ存在する置換基であり、Ｒ⁵、Ｒ⁸は、Ｘ¹またはＸ²がＣ原子の場合のみ存在する置換基である。Ｘ¹がＣ原子の場合は、Ｘ¹、Ｒ³、Ｒ⁴およびＲ⁵が、Ｘ²がＣ原子の場合は、Ｘ²、Ｒ⁶、Ｒ⁷およびＲ⁸が、それぞれ共同で飽和または部分的にもしくは完全に不飽和の環状構造を形成してもよい。Ｘ¹がＮ原子の場合は、Ｘ¹、Ｒ³およびＲ⁴が、Ｘ²がＮ原子の場合は、Ｘ²、Ｒ⁶およびＲ⁷が、それぞれ共同で飽和または部分的にもしくは完全に不飽和の環状構造を形成してもよい。更に、点線は、共役構造を示す。]

[Substituents R ^{1 to} R ⁸ in the formula are independent of each other and may be the same or different. Substituents R ^{1 to} R ⁸ are each an H atom, a C _{1 to} C ₃₀ straight chain or an alkyl group having a side chain, a C _{2 to} C ₃₀ single chain or a straight chain having a plurality of double bonds, or An alkenyl group having a side chain, a linear or side chain alkynyl group having a single or multiple triple bond of C _{2 to} C ₃₀ , a saturated or partially or fully unsaturated cycloalkyl group, an aryl group And any of heterocyclic groups. Further, the H atom contained in one or a plurality of substituents among these substituents R ^{1 to} R ⁸ can be partially or completely substituted by a halogen atom, or can be partially substituted by a CN group or NO ₂ group. Can be substituted. Moreover, arbitrary substituents among the substituents R ^{1 to} R ⁸ may jointly form a cyclic structure. The carbon atoms contained in these substituents R ^{1 to} R ⁸ are —O—, —Si (R ′) ₂ —, —C (O) —, —C (O) O—, —S—, -S (O)-,-SO ₂ -,-SO ₃ -,-N =,-N = N-,-NH-,-NR '-,-PR'-,-P (O) R'-, Can be substituted by atoms and / or groups selected from the group -P (O) R'-O-, -OP (O) R'-O-, and -P (R ') ₂ = N- (where , R ′ is an alkyl group having a C _{1 to} C ₁₀ linear or side chain, an alkyl group partially or completely substituted by an F atom, a saturated or partially or fully unsaturated cycloalkyl group , An unsubstituted or substituted phenyl group, or an unsubstituted or substituted heterocycle). X ¹ and X ² each independently represent an N atom, an O atom, or a C atom. R ⁴ and R ⁷ are substituents which are present only when X ¹ or X ² is an N atom or a C atom, and R ⁵ and R ⁸ are present only when X ¹ or X ² is a C atom. It is a substituent. When X ¹ is a C atom, X ¹ , R ³ , R ⁴ and R ⁵ are saturated or partially together when X ² is a C atom, X ² , R ⁶ , R ⁷ and R ⁸ are each independently saturated or partially Alternatively, a completely unsaturated cyclic structure may be formed. When X ¹ is an N atom, X ¹ , R ³ and R ⁴ are together, and when X ² is an N atom, X ² , R ⁶ and R ⁷ are jointly saturated or partially or completely unsaturated. A saturated ring structure may be formed. Furthermore, a dotted line shows a conjugate structure. ]

  That is, the present invention relates to “an ionic liquid containing a sulfonium ion containing one, two or three S—N bonds as a cation component” and “an ionic liquid containing an organic substance represented by the general formula (1) as a cation component”. And “an ionic liquid comprising a cation component and an anion component, wherein the cation component is one or more of the organic substances represented by the general formula (1)”. Is achieved.

ADVANTAGE OF THE INVENTION According to this invention, while exhibiting a stable liquid state in a wide temperature range, the ionic liquid excellent in electrochemical stability can be provided.
The ionic liquid of the present invention includes a lithium secondary battery, an electric double layer capacitor, a fuel cell, a dye-sensitized solar cell, an electrolyte for a storage device, an electrolytic solution or an additive, a reaction, a separation / extraction solvent, a sensor, an electrolytic plating, It can be applied to polymers, plasticizers, lubricants, actuators and the like.

As the cation component represented by the general formula (1), the substituents R ^{1 to} R ⁸ in the general formula (1) are H atoms, alkyl groups having a C _{1 to} C ₃₀ linear or side chain. A saturated or partially or fully unsaturated cycloalkyl group, aryl group, or heterocyclic group, and included in one or more substituents among these substituents R ^{1 to} R ⁸ The H atom is preferably partially or completely substituted with a halogen atom, or partially substituted with a CN group or NO ₂ group. Furthermore, the carbon atoms contained in these substituents R ^{1 to} R ⁸ are —O—, —Si (R ′) ₂ —, —C (O) —, —C (O) O—, —S—, -S (O) -, and -NR '- [wherein, R' is an alkyl group or partially or completely substituted alkyl groups by F atoms, a straight chain or a side chain of C ₁ -C ₁₀ , Saturated or partially or fully unsaturated cycloalkyl groups, unsubstituted or substituted phenyl groups, or unsubstituted or substituted heterocycles. It is preferably one substituted with an atom and / or an atomic group selected from the group of More preferably, R ^{1 to} R ⁸ in the general formula (1) are each an alkyl group or an alkoxy group having a linear or side chain of C _{1 to} C ₂₀ (R ^{1 to} R ⁸ are the same or different from each other). May be).

The anion component used in the present invention includes [RSO ₃ ] ⁻ , [Rf SO ₃ ] ⁻ , [(RfSO ₂ ) ₂ N] ⁻ , [(FSO ₂ ) ₂ N] ⁻ , [(RfSO ₂ ) ₃ C]. ^- , [(FSO ₂ ) ₃ C] ^- , [ROSO ₃ ] ^- , [RC (O) O] ^- , [Rf C (O) O] ^- , [CCl ₃ C (O) O] ^- , [( CN) ₃ C] ^- , [(CN) ₂ CR] ^- , [(RO (O) C) ₂ CR] ^- , [R ₂ P (O) O] ^- , [RP (O) O ₂ ] ^2- , [(RO) ₂ P (O) O] ^- , [(RO) P (O) O ₂ ] ^2- , [(RO) (R) P (O) O] ^- , [Rf ₂ P (O) ^{O] -, [RfP (O} ) O 2] 2-, [(RfO) 2 P (O) O] - [B (OR) 4] -, BRf 4 -, [N (CF 3) 2] -, ^{_{[N (CN) 2] -}} , [AlCl 4] -, PF 6 -, [RfPF 5] -, [Rf 3 PF 3] -, BF 4 -, [RfBF 3] -, SO 4 2-, HSO 4 ^{_{-, NO 3 -, F -}} , Cl -, Br -, and I ^- [each substituent R in the formula, H atom, a halogen atom, a linear or alkyl radical with a side chain of C ₁ -C ₁₀ An alkenyl group having a straight chain or a side chain having a single or plural double bonds of C _{2 to} C ₁₀ , a straight chain or a side chain having a single or plural triple bonds of C _{2 to} C ₁₀ Alkynyl group, saturated or partially if Represents any of the cycloalkyl groups fully unsaturated. The H atom contained in these substituents R can be partially or completely substituted by a halogen atom, or partially substituted by a CN group or NO ₂ group. The carbon atoms contained in these substituents R are -O-, -C (O)-, -C (O) O-, -S-, -S (O)-, -SO ₂ -,- SO ₃ -,-N =,-N = N-,-NR '-,-N (R') ₂ , -PR '-,-P (O) R'-,-P (O) R'-O -, -OP (O) R'-O-, and -P (R ') ₂ = can be substituted by atoms and / or atomic groups selected from the group N- (where R' is C ₁ -C ₁₀ An alkyl group having a straight chain or a side chain, or an alkyl group partially or fully substituted by an F atom, a saturated or partially or fully unsaturated cycloalkyl group, an unsubstituted or substituted phenyl group Or an unsubstituted or substituted heterocycle. Rf is a fluorine-containing substituent. ] Or one or more species selected from the group of These anionic components exist as a stable liquid in a wide temperature range by combining with the cation component, and can constitute an ionic liquid having excellent electrochemical stability. Here, “present as a stable liquid in a wide temperature range” means that the liquid is near 100 ° C., which is currently defined as a general ionic liquid, and the thermal decomposition temperature is about 200 ° C. higher than the melting point, In other words, it means that it exists as a stable liquid in this wide temperature range.

The preferred types of these anion components used as the counter ion of the general formula (1) are [RSO ₃ ] ⁻ , [RfSO ₃ ] ⁻ , [(RfSO ₂ ) ₂ N] ⁻ , [(FSO ₂ ) _2. ^{N] -, RfCOO -, [} (RfO) 2 P (O) O] - PF 6 -, BF 4 -, [RfBF 3] -, [B (OR) 4] -, [N (CN) 2] - , [AlCl ₄ ] ⁻ , SO ₄ ²⁻ , HSO ₄ ⁻ , NO ₃ ⁻ , F ⁻ , Cl ⁻ , Br ⁻ , and I ⁻ , and more preferably, ^{_{[RSO 3] -, [RfSO}} 3] -, [(RfSO 2) 2 N] -, [(FSO 2) 2 N] -, RfCOO -, [(RfO) 2 P (O) O] -, PF 6 ^{_{-, BF 4 -, [RfBF}} 3] -, [B (oR) 4] -, [N (CN) 2] -, [AlCl 4] -, SO 4 2-, HSO 4 -, and NO ₃ ^- in One or more species selected from the group.
The combination of the cation component and these preferable anion components can form an ionic liquid that exhibits more preferable characteristics, that is, a stable liquid in a wide temperature range from a low temperature and is excellent in electrochemical stability.

Moreover, the anion component which is a counter ion of the general formula (1) is [RSO ₃ ] ⁻ , [Rf SO ₃ ] ⁻ , [(Rf SO ₂ ) ₂ N] ⁻ , [(FSO ₂ ) ₂ N] ^{−. , RfCOO -, [(RfO)} 2 P (O) O] -, PF 6 -, BF 4 -, [RfBF 3] -, [B (OR) 4] -, [N (CN) 2] -, [ AlCl ₄ ] ⁻ , SO ₄ ²⁻ , HSO ₄ ⁻ , NO ₃ ⁻ , F ⁻ , Cl ⁻ , Br ⁻ , and I ^−. R ^{1 to} R ⁸ in 1) are each an H atom, an alkyl group or an alkoxy group having a linear or side chain of C _{1 to} C ₁₀ (R ^{1 to} R ⁸ may be the same or different from each other). The ionic liquid is particularly preferred.

Further, by reducing the symmetry of the cation in the general formula (1), for example, by making at least one of R ^{1 to} R ⁸ different, a low melting point ionic liquid can be obtained.
Therefore, when it is desired to constitute an ionic liquid that focuses on a low melting point, at least one of R ^{1 to} R ^{8 in} the general formula (1) is an alkyl group having a linear or side chain of C _{4 to} C ₂₀ or an alkoxy group, the remaining R ^n, or ionic liquid having a cation component which is a linear alkyl group of H atom or a C ₁ -C _4, at least one silyl group or ring structure of R ¹ to R ⁸ An ionic liquid having a cation component in which the remaining R ⁿ is an H atom or a C _{1 to} C ₄ linear alkyl group.
Moreover, as the anion component to be combined with these cations, any one of [(CF ₃ SO ₂ ) ₂ N] ⁻ , PF ₆ ^— and BF ₄ is preferable. Such an ionic liquid having a low melting point can be used as an electrolyte alone, or can be used as a reaction solvent at a low temperature.

The ionic liquid of the present invention described above is an ionic liquid that is stable in a wide temperature range and excellent in electrochemical stability. Therefore, the ionic liquid of the present invention is used for electrolytes, electrolytic solutions or additives for power storage devices, lithium secondary batteries, electric double layer capacitors, fuel cells or dye-sensitized solar cells, actuators, and lubricating oils. It is useful as a material and as a reaction solvent used for various reactions. Furthermore, since it is stable against strong alkali, it can also be used as an alkaline atmosphere reaction solvent. It has been known that the thermal stability is remarkably increased by using an ionic liquid instead of a conventionally used plasticizer.
Electrodeposition of aluminum alloys such as Al, Al—Mn, Al—Ti, Al—Mg, and Al—Cr in ionic liquids has been reported.
By polymerizing the ionic liquid, it is possible to design a polymer material having specific properties such as flame retardancy and electrochemical stability of the ionic liquid containing ions at high density.
In addition, although the cation shown in the general formula (1) is represented as a sulfonium cation having a positive charge on the S atom for convenience, it is considered that the charge is delocalized in the molecule.

A typical method for synthesizing an ionic liquid containing the cation component represented by the general formula (1) is shown below.
As shown below, the ionic liquid containing the cation component represented by the general formula (1) is obtained by alkylation.

An alkylating agent (R ⁶ W) is added dropwise to the organic material represented by the general formula (2) as a raw material, and reacted for a predetermined temperature and time. After washing with ultrapure water or diethyl ether, it is vacuum dried. Examples of the alkylating agent (R ⁶ W) include alkyl iodide, alkyl bromide, alkyl chloride, dialkyl sulfate, sulfonic acid dialkyl ester, carbonic acid dialkyl ester, phosphoric acid trialkyl ester, mono- or poly-fluoroalkylsulfonic acid. Examples thereof include alkyl esters, perfluoroalkylsulfonic acid alkyl esters, mono- or poly-fluorocarboxylic acid alkyls, perfluorocarboxylic acid alkyls, sulfuric acid, nitric acid, and hydrochloric acid.

  The ionic liquid containing the cation component represented by the general formula (1) can also be obtained by amination.

ただし、Ｒ¹＝Ｒ²でもよい。

However, R ¹ = R ² may be used.

  The aminating agent (5) is dropped into the organic material represented by the general formula (3) as a raw material, and reacted for a predetermined temperature and time. After washing with ultrapure water or diethyl ether, it is vacuum dried. Examples of the aminating agent (5) include amine chloride, amine bromide and amine iodide.

  Moreover, it is also possible to make the ionic liquid which has a different anion by anion exchange by the following method.

Here, as the ion-binding compound A ⁺ Q ⁻ , for example, LiN (CF ₃ SO ₂ ) ₂ , LiN (FSO ₂ ) ₂ , NaN (CF ₃ SO ₂ ) ₂ , KN (CF ₃ SO ₂ ) ₂ , CF ₃ SO ₃ Li, CF ₃ SO ₃ Na, CF ₃ CF ₂ CF ₂ CF ₂ SO ₃ Li, CF ₃ SO ₃ K, CF ₃ CH ₂ SO ₃ Li, CF ₃ CH ₂ SO ₃ Na, CF ₃ CH _{2 SO 3 K, CF 3 COOLi,} CF 3 COONa, CF 3 COOK, CF 3 COOAg, CF 3 CF 2 CF 2 COOAg, (CF 3 CH 2) 2 POOLi, LPF 6, NaPF 6, KPF 6, LiBF 4, NaBF ₄ , KBF ₄ , NH ₄ BF ₄ , KC ₂ F ₅ BF ₃ , LiB (C ₂ O ₄ ) ₂ , LiSbF ₆ , NaSbF ₆ , KSbF ₆ , NaN (CN) ₂ , AgN (CN) ₂ , Na ₂ SO _4, K ₂ SO _4, NaN _3, KNO ₃ and the like, but not limited to the above compounds.

Formula (4) substituents R ¹ to R ⁸ and Formula (6) in in the substituent R ¹ to R ⁸ are independent of each other, it may be be the same or different. Each of these substituents is an H atom, a halogen atom, a C ₁ -C ₃₀ straight chain or an alkyl group having a side chain, a C ₂ -C ₃₀ straight chain having a single bond or a plurality of double bonds, or An alkenyl group having a side chain, a linear or side chain alkynyl group having a single or multiple triple bond of C _{2 to} C ₃₀ , a saturated or partially or fully unsaturated cycloalkyl group, an aryl group And any of heterocyclic groups. In addition, the H atom contained in one or a plurality of substituents among these substituents can be partially or completely substituted with a halogen atom, or can be partially substituted with a CN group or a NO ₂ group. Arbitrary substituents may jointly form a cyclic structure. The carbon atoms contained in these substituents are -O-, -Si (R ') _2- , -C (O)-, -C (O) O-, -S-, -S (O)-, -SO ₂ -,-SO ₃ -,-N =,-N = N-,-NH-,-NR '-,-PR'-,-P (O) R '-,-P (O) R' -O-, -OP (O) R'-O-, and -P (R ') ₂ = can be substituted by atoms and / or groups selected from the group N-, where R' is C _1- An alkyl group having a C ₁₀ linear or side chain, or an alkyl group partially or fully substituted by an F atom, a saturated or partially or fully unsaturated cycloalkyl group, unsubstituted or substituted Represents a phenyl group, or an unsubstituted or substituted heterocycle).

Examples of the halogen atom include F, Cl, Br, and I.
Examples of the cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, and the like. In addition, the cycloalkyl group includes those having an unsaturated bond such as a cycloalkenyl group and a cycloalkynyl group, and can be partially or completely substituted by a halogen atom, or can be partially substituted by a CN group or a NO ₂ group. Can be substituted.

  Examples of the heterocyclic group include pyrrolidinyl, pyrrolinyl, imidazolidinyl, imidazolinyl, pyrarozolidinyl, pyrazonyl, piperidyl, piperazinyl, morpholinyl, and thienyl groups. These heterocyclic groups may contain one or more alkyl groups, alkoxy groups, hydroxyl groups, carboxyl groups, amino groups, alkylamino groups, dialkylamino groups, thiol groups, alkylthio groups, and halogen atoms. Good.

  In addition, the aryl group includes phenyl, cumenyl, mesityl, tolyl, xylyl group and the like (these aryl groups include an alkyl group, an alkoxy group, a hydroxyl group, a carboxyl group, an acyl group, a formyl group, an amino group, and an alkylamino group. , A dialkylamino group, a thiol group, an alkylthio group, and a halogen atom may be contained.

  Further, alkoxyalkyl groups such as methoxymethyl, methoxyethyl, ethoxymethyl, and ethoxyethyl, and trialkylsilyl groups such as trimethylsilyl group can be exemplified.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to these Examples.

Example 1
(a) Preparation of bis (diethylamino) sulfide 78 ml (750 mmol) of diethylamine, 25 g (100 mmol) of sodium thiosulfate pentahydrate and 1 L of hexane were charged into an eggplant flask and 3 ml of a hexane solution of 11 ml (200 mmol) of bromine was added at 5 ° C. Drip slowly over time. After dropping, the mixture was stirred at room temperature for 12 hours. The filtrate was concentrated under reduced pressure, and purified by distillation under reduced pressure (1 kPa, 54-63 ° C.). As a yellow transparent liquid, 9.7 g of bis (diethylamino) sulfide was obtained. The yield was 55%.
The compound was identified with a nuclear magnetic resonance analyzer (BRUKER Ultra Shield 300 NMR Spectrometer manufactured by BRUKER). The spectrum data is shown below.
¹ H-NMR (300 MHz, solvent: CDCl ₃ , standard substance: tetramethylsilane)
δ3.08 (m, 8H)
1.14 (t, 12H)
The structural formula is shown below.

(B) Preparation of diethylamine chloride 1.05 ml (10 mmol) of diethylamine and 25 ml of CH ₂ Cl ₂ were charged into an eggplant flask, and 1.09 ml (10 mmol) of t-butyl hypochlorite was added dropwise under ice cooling. The mixture was stirred for 1 hour under ice cooling.
The compound was identified with a nuclear magnetic resonance analyzer (BRUKER Ultra Shield 300 NMR Spectrometer manufactured by BRUKER). The spectrum data is shown below.
¹ H-NMR (300 MHz, solvent: CDCl ₃ , standard substance: tetramethylsilane)
δ3.00 (m, 4H)
1.23 (t, 6H)
The structural formula is shown below.

(C) Preparation of tris (diethylamino) sulfonium bistrifluoromethanesulfonylimide 0.8 g (5 mmol) of bis (diethylamino) sulfide obtained in (a) into a CH ₂ Cl ₂ solution of diethylamine chloride (reaction solution of (b)) Was added dropwise and stirred at room temperature for 2 days. After extraction with ultra pure water, the aqueous layer was washed with CH ₂ Cl ₂ . While stirring the aqueous layer, an aqueous solution of LiTFSI 1.3 g (4.5 mmol) was added dropwise and stirred at room temperature for 3 days. The mixture was extracted with dichloromethane, washed with water, and purified by a silica gel column using CH ₂ Cl ₂ as a developing solvent. As a yellow transparent liquid, 1.2 g of tris (diethylamino) sulfonium bistrifluoromethanesulfonylimide was obtained. The yield was 45%.
The compound was identified with a nuclear magnetic resonance analyzer (BRUKER Ultra Shield 300 NMR Spectrometer manufactured by BRUKER). The spectrum data is shown below.
¹ H-NMR (300 MHz, solvent: CDCl ₃ , standard substance: tetramethylsilane)
δ3.00 (m, 12H)
1.26 (t, 18H)
¹⁹ F-NMR (282 MHz, solvent: CDCl ₃ , standard substance: CF ₃ Cl)
δ-78.47 (s, 6F)
The structural formula is shown below (the dotted line in the formula indicates a conjugated structure).

  The melting point was measured with a scanning differential calorimeter (DSC8230, manufactured by Shimadzu Corporation). The melting point was 18.2 ° C and the crystallization temperature was -2.8 ° C. The thermal decomposition temperature with a thermogravimetric analyzer (TG8120 manufactured by Rigaku Corporation) was measured. The 5% weight loss temperature measured at a heating rate of 10 ° C./min was 211.0 ° C.

(C) Preparation of dimethyl (diethylamino) sulfonium bistrifluoromethanesulfonylimide 2.1 ml (30 mmol) of dichloromethane and diethylamine were charged into an eggplant flask, and 2.3 ml (30 mmol) of t-butyl hypochlorite was added dropwise at 0 ° C. After stirring for 1 hour, 2.1 ml (20 mmol) of dimethyl sulfide was added dropwise at 0 ° C. After dropping, the mixture was stirred overnight at room temperature. After confirming the progress of the reaction by NMR, extraction with water and an aqueous solution of LiTFSI 8.6 g (30 mmol) were added. Extraction with dichloromethane, washing with water and concentration gave a yellow transparent liquid.
The compound was identified with a nuclear magnetic resonance analyzer (BRUKER Ultra Shield 300 NMR Spectrometer manufactured by BRUKER). The spectrum data is shown below.
¹ H-NMR (300 MHz, solvent: CDCl ₃ , standard substance: tetramethylsilane)
δ3.26 (m, 4H)
3.04 (s, 6H)
1.26 (t, 6H)
¹⁹ F-NMR (282 MHz, solvent: CDCl ₃ , standard substance: CF ₃ Cl)
δ-78.47 (s, 6F)
The structural formula is shown below.

  The thermal decomposition temperature with a thermogravimetric analyzer (TG8120 manufactured by Rigaku Corporation) was measured. The 5% weight loss temperature measured at a heating rate of 10 ° C./min was 205.8 ° C.

Claims (5)

An ionic liquid comprising a cation component and an anion component, wherein the cation component is one or a plurality of organic substances represented by the following general formula (1), and the anion component is [(CF ₃ SO ₂ ) ₂ N] ⁻ An ionic liquid.

[Substituents R ^{1 to} R ⁸ in the formula are independent of each other and may be the same or different. The substituents R ^{1 to} R ⁸ each represent an H atom, an alkyl group having a C _{1 to} C ₃₀ linear or side chain. X ¹ and X ² each independently represent an N atom or a C atom. R ⁵ and R ⁸ are substituents present only when X ¹ or X ² is a C atom. Furthermore, a dotted line shows a conjugate structure. ] 2. The ionic liquid according to claim 1, wherein the substituents R ^{1 to} R ⁸ in the general formula (1) are each an alkyl group having a linear or side chain of C _{1 to} C ₂₀ . 2. The ionic liquid according to claim 1, wherein the substituents R ^{1 to} R ⁸ in the general formula (1) are alkyl groups having a C _{1 to} C ₁₀ linear or side chain, respectively. The organic matter represented by the following following general formula (1) A method for producing an ionic liquid comprising a cation component, wherein the general formula, wherein alkylation reaction of a compound represented by the following general formula (2) as a raw material ( A method for producing an ionic liquid containing the organic substance represented by 1) as a cation component.

[Substituents R ^{1 to} R ⁸ in the formula are independent of each other and may be the same or different. The substituents R ^{1 to} R ⁸ each represent an H atom, an alkyl group having a C _{1 to} C ₃₀ linear or side chain. X ¹ and X ² each independently represent an N atom or a C atom. R ⁵ and R ⁸ are substituents present only when X ¹ or X ² is a C atom. Furthermore, a dotted line shows a conjugate structure. ]

[Substituents R ^{1 to} R ⁵ in the formula are independent of each other and may be the same or different. The substituents R ^{1 to} R ⁵ each represent an H atom and an alkyl group having a C _{1 to} C ₃₀ linear or side chain. X ¹ represents an N atom or a C atom. R ⁵ is a substituent that exists only when X ¹ is a C atom. ] The organic matter represented by the following following general formula (1) A method for producing an ionic liquid comprising a cation component, wherein the general formula, wherein amination of the compound represented by the following general formula (3) as a raw material ( A method for producing an ionic liquid containing the organic substance represented by 1) as a cation component.

[Substituents R ^{1 to} R ⁸ in the formula are independent of each other and may be the same or different. The substituents R ^{1 to} R ⁸ each represent an H atom, an alkyl group having a C _{1 to} C ₃₀ linear or side chain. X ¹ and X ² each independently represent an N atom or a C atom. R ⁵ and R ⁸ are substituents present only when X ¹ or X ² is a C atom. Furthermore, a dotted line shows a conjugate structure. ]

[Substituents R ^{3 to} R ⁸ in the formula are independent of each other and may be the same or different. The substituents R ^{3 to} R ⁸ each represent an H atom, an alkyl group having a C _{1 to} C ₃₀ linear or side chain. X ¹ and X ² each independently represent an N atom or a C atom. R ⁵ and R ⁸ are substituents present only when X ¹ or X ² is a C atom. ]