JP4822269B2 - New onium salt - Google Patents

Description

  The present invention relates to a novel onium salt that can be applied as a reaction solvent and a reaction catalyst in the field of organic synthesis, and an ionic liquid of a lithium ion battery or an electric double layer capacitor in the field of electrochemistry.

  Onium salts consisting of onium cations such as ammonium ions and phosphonium ions and counterions such as tetrafluoroborate and hexafluorophosphate have physical properties (melting point, electrical conductivity, solubility in water and organic solvents, etc.) However, it has various physical properties depending on the chain length and molecular structure of the alkyl group on the onium cation side and the type of the counter anion, so that it is applied to various fields.

That is, those having a relatively high melting point (100 ° C. or higher) are used as PTC catalysts and supporting electrolytes in the synthetic chemistry and electrochemical fields, respectively, and those having a relatively low melting point (100 ° C. or lower) are ionic liquids. It is also known as the “material chemistry” field.
In other words, those with a relatively low melting point (100 ° C or lower) have high thermal stability, negligibly low vapor pressure, low toxicity, and electrochemical characteristics, so they are used in organic synthesis and extraction. Research has been actively conducted as green alternatives of organic organic solvents (Non-patent Document 1).

  Examples of such onium salts include 1,3-dialkylimidazolium cations (dialkyl groups mean asymmetric dialkyl substituents in which the two alkyl groups have different chain lengths, and the imidazolium parent nucleus is substituted with alkyl substituents. N-alkylpyridium cations (including one or more substituted alkyl groups on the pyridium nucleus), N, N-dialkylpiperidium cations, N, N-dialkylpyrrolidiniums Halogenation of onium cations and tetrafluoroborate, hexafluorophosphate, chlorinated anions, and iodide anions selected from quaternary ammonium cations and quaternary phosphonium cations having cations, alkyl substituents, etc. Substance anion, trifluoromethanesulfonic acid anion and N, N-bistrifluoromethane Those comprising a combination of a counter anion selected from such anions such sulfonic acid imide are known.

  In general, onium salts can be used to create ionic liquids with new physical properties by combining cations and anions. Therefore, ionic liquids are also called “Designer Solvents,” and the concept of Green Chemistry Rapid research has been developed as a substance that meets the requirements.

  However, even with the same homologue (for example, imidazolium salt), regarding its physical properties (for example, melting point, electrical conductivity, etc.), it is difficult to determine whether or not it becomes an ionic liquid from its structure. In order to investigate, it is necessary to actually synthesize and examine.

  Conventionally, a wide variety of onium ions that become cations among the ion pairs that become combinations have been studied.

However, regarding anions, halide anions, trifluoromethanesulfonic acid anions, N, N-bistrifluoromethanesulfonic acid imide anions (Patent Document 1), and recently, fluoroanions [F (HF) _n ⁻ : n = 2-3] (Non-patent document 2), hexafluoroniobate (NbF ₆ ⁻ ), hexafluorotantalate (TlF ₆ ⁻ ) (non-patent document 3), oxypentafluorotungstate (WOF ₅ ⁻ ) ( Non-Patent Document 4), mono (perfluoroalkylsulfonyl) -2,3,4,5,6-pentasubstituted phenylmethanide anion and bis (perfluoroalkylsulfonyl) -2,3,4,5,6-pentasubstituted phenyl Only limited anions such as the methanide anion (Patent Document 2) have been studied.

  Therefore, in order to create an onium salt that can be used in various applications, new anions that have not received much attention have been developed, and these have been used as counter anions to form new combinations with conventionally known onium ions. The development of a new onium salt by was desired.

JP 2004-43407 A JP 2004-307446 A IonicLiquids as Green Solvents: Progress and Prospects, Ed. By R. D. Rogers, K. R. Seddon, ACS: Washington, DC, Oxford University Press (2003) J. Fluorine Chemistry, 105, 221-2227 (2000) J. Fluorine Chemistry, 115, 133-135 (2002) J. Fluorine Chemistry, 126, 1095-1100 (2005)

  The present invention can be applied to various fields. For example, in the organic synthesis field, it is useful as a reaction solvent, a reaction catalyst, and the like, and as an ionic liquid of a lithium ion battery and an electric double layer capacitor in the electrochemical field. The object is to provide an onium salt.

  In order to prepare a novel onium salt, the present inventors paid attention to sulfonic acids having a bulky nitrogen-containing perfluoroalkyl group and imides containing them, and used them as counter anions (nitrogen-containing perfluoroalkanesulfonic acid, and It has been found that a highly useful onium salt can be obtained by using it as an imide salt containing it, and the present invention has been completed.

（式中のＣ^＋はオニウムカチオンであり、R_f ¹とR_f ^２はそれぞれ同一又は互いに異なる炭素数１〜５のペルフルオロアルキル基であって、両者は直接に、あるいは酸素原子又は窒素原子を介して結合し、両者が結合している窒素原子とともに複素環を形成してもよい。R_f ³は炭素数が１〜４の分岐状もしくは直鎖状ペルフルオロアルキレン基を示す）で表される含窒素ペルフルオロアルカンスルホン酸塩。
〈２〉 一般式（２）

（式中のR^１〜R^５はそれぞれ独立に水素、アルキル基、アルケニル基、アリール基又はアラルキル基であり、これらの基は置換されていてもよい。R_f ¹、R_f ^２及びR_f ³は一般式（１）と同じである）で示される含窒素ペルフルオロアルカンスルホン酸塩。
〈３〉 一般式（３）

（式中のR^１〜R^４はそれぞれ独立に水素、アルキル基、アルケニル基、アリール基又はアラルキル基であり、これらの基は置換されていてもよい。R_f ¹、R_f ^２及びR_f ³は一般式（１）と同じである）で示される新規含窒素ペルフルオロアルカンスルホン酸塩。
〈４〉 一般式（４）

（式中のR^１〜R^４はそれぞれ独立に水素、アルキル基、アルケニル基、アリール基又はアラルキル基であり、これらの基は置換されていてもよい。R_f ¹、R_f ^２及びR_f ³は一般式（１）と同じである）で示される含窒素ペルフルオロアルカンスルホン酸塩。
〈５〉 一般式（５）

（式中のR^１〜R^５、並びにR_f ¹、R_f ^２及びR_f ³は一般式（１）と同じである。R_f ^４は炭素数が１〜４の直鎖状ペルフルオロアルキル基か、又はイミド塩のもう一方の構成要素である含窒素ペルフルオロアルカン基と同一であってもよい）で示される含窒素ペルフルオロアルカンスルホン酸塩。 That is, according to this application, the following invention is provided.
<1> General formula (1)

(In the formula, C ⁺ is an onium cation, and R _f ¹ and R _f ² are the same or different C 1-5 perfluoroalkyl groups, both of which are directly or oxygen atom or nitrogen atom. And may form a heterocyclic ring together with the nitrogen atom to which both are bonded, and R _f ³ represents a branched or linear perfluoroalkylene group having 1 to 4 carbon atoms). Nitrogen-containing perfluoroalkane sulfonate.
<2> General formula (2)

(Wherein R ^{1 to} R ⁵ are each independently hydrogen, an alkyl group, an alkenyl group, an aryl group or an aralkyl group, and these groups may be substituted. R _f ¹ , R _f ² and R _f ³ is the same nitrogen-containing perfluoroalkanesulfonic acid salt represented by the general formula (1).
<3> General formula (3)

(Wherein R ^{1 to} R ⁴ are each independently hydrogen, an alkyl group, an alkenyl group, an aryl group or an aralkyl group, and these groups may be substituted. R _f ¹ , R _f ² and R _f ³ is the same nitrogen-containing perfluoroalkanesulfonic acid salt represented by the general formula (1).
<4> General formula (4)

(Wherein R ^{1 to} R ⁴ are each independently hydrogen, an alkyl group, an alkenyl group, an aryl group or an aralkyl group, and these groups may be substituted. R _f ¹ , R _f ² and R _f ³ is the same nitrogen-containing perfluoroalkanesulfonic acid salt represented by the general formula (1).
<5> General formula (5)

(Wherein R ^{1 to} R ⁵ , R _f ¹ , R _f ² and R _f ³ are the same as those in the general formula (1). R _f ⁴ is a linear perfluoroalkyl group having 1 to 4 carbon atoms. Or a nitrogen-containing perfluoroalkanesulfonic acid salt represented by the same formula as the nitrogen-containing perfluoroalkane group that is the other component of the imide salt.

  The novel onium salt according to the present invention has different melting points (liquid at room temperature) by combining onium ions (cations such as ammonium and phosphonium) and counter anions (the above nitrogen-containing perfluoroalkanesulfonic acid and imide salts containing the same). For example, an onium salt having a high melting point is used as a supporting electrolyte in the electrochemical field, and an onium salt having a low melting point is an organic synthesis process that does not use a volatile organic solvent. It is extremely useful industrially in the fields of organic chemistry and electrochemistry.

Problem embodiment

  The onium salt of the present invention is represented by the general formulas (1) to (5), and contains the following nitrogen-containing perfluoroalkanesulfonic acid and an imide containing the same as a counter anion. .

（式中のR_f ¹とR_f ^２それぞれ同一又は互いに異なる炭素数１〜５のペルフルオロアルキル基であって、両者は直接に、あるいは酸素原子又は窒素原子を介して結合し、両者が結合している窒素原子とともに複素環を形成してもよい。R_f ³は炭素数が１〜４の分岐状もしくは直鎖状ペルフルオロアルキレン基を示す）

(In the formula, R _f ¹ and R _f ² are the same or different perfluoroalkyl groups having 1 to 5 carbon atoms, and both are bonded directly or through an oxygen atom or a nitrogen atom. A heterocyclic ring may be formed together with the nitrogen atom in which R _f ³ represents a branched or linear perfluoroalkylene group having 1 to 4 carbon atoms.

（式中のRf¹、Rf^２、Rf^３は一般式６に記載のものと同一であり、Rf^４は炭素数が１〜４の直鎖状ペルフルオロアルキル基か、又はイミド塩のもう一方の構成要素である含窒素ペルフルオロアルカン基を意味し、その場合に、対称でも非対称でもよい）

(In the formula, Rf ¹ , Rf ² and Rf ³ are the same as those described in formula 6, and Rf ⁴ is a linear perfluoroalkyl group having 1 to 4 carbon atoms, or the other of the imide salt. (This means a nitrogen-containing perfluoroalkane group as a constituent element, in which case it may be symmetric or asymmetric)

Examples of (R _f ¹ ) (R _f ² ) N- include the following.

Further, examples of R _f ^3, it is illustrated as follows.

  The nitrogen-containing perfluoroalkane sulfonate is synthesized by electrolytic fluorination of 1) nitrogen-containing perfluoroalkane sulfonic acid fluoride by the corresponding nitrogen-containing alkane sulfonic acid chloride / hydrochloride, which is then hydrolyzed with sulfonic acid. 2) It can be easily synthesized by using the corresponding nitrogen-containing perfluoroalkane halide as a raw material and subjecting it to a sulfinylation reaction. The method preferably employed in the present invention is the method 2).

The counter cation constituting the onium salt represented by the general formulas (1) to (5) according to the present invention is an onium cation represented by [C] ⁺ .
Examples of onium cations include imidazolium, piperidinium, pyridinium, morpholium, pyrrolidinium, 1,5-diazabicyclo [4.3.0] -5-nonenium, 1,8-diazabicyclo [5,4,0] -7-undecenium. Cations derived from nitrogen heterocyclic compounds, quaternary organic ammonium and quaternary organic phosphonium are included.
The onium cation preferably used in the present invention is an imidazolium-derived cation represented by the following general formula, a quaternary organic ammonium, and a quaternary organic phosphonium.

（式中、R^１〜R^５はそれぞれ独立に水素、アルキル基、アルケニル基、アリール基又はアラルキル基であり、これらの基は置換されていてもよい。）

(In the formula, R ^{1 to} R ⁵ are each independently hydrogen, an alkyl group, an alkenyl group, an aryl group or an aralkyl group, and these groups may be substituted.)

（式中、R^１〜R^４はそれぞれ独立に水素、アルキル基、アルケニル基、アリール基又はアラルキル基であり、これらの基は置換されていてもよい。）

(Wherein R ^{1 to} R ⁴ are each independently hydrogen, an alkyl group, an alkenyl group, an aryl group or an aralkyl group, and these groups may be substituted.)

（式中、R^１〜R^４はそれぞれ独立に水素、アルキル基、アルケニル基、アリール基又はアラルキル基であり、これらの基は置換されていてもよい。）

(Wherein R ^{1 to} R ⁴ are each independently hydrogen, an alkyl group, an alkenyl group, an aryl group or an aralkyl group, and these groups may be substituted.)

In R ^{1 to} R ⁵ , the alkyl group includes methyl, ethyl, hydroxyethyl, 2-chloroethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, A butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group or the like having a linear or branched chain of up to 30 carbon atoms, such as a vinyl group, an allyl group, etc. As an aryl group, a phenyl group, a pentamethylphenyl group, a toluyl group, a xylyl group, a naphthyl group, etc., and as an aralkyl group, a benzyl group, an o-toluylmethyl group, an m-toluylmethyl group, a p-toluylmethyl group , 2-phenylethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group and the like.

（式中、Rf¹、Rf^２、Rf^３は一般式（１）に記載のものと同一であり、Ｍはアルカリ金属、又は１価に相当するアルカリ土類金属である。［Ｃ］^＋はオニウムカチオンであり、Ｘはハロゲン原子である） The novel onium salt having the nitrogen-containing perfluoroalkanesulfonic acid occupied by the general formula (1) according to the present invention as an anion is, for example, a readily available onium salt anion (halide anion) as a molten salt. It can be easily synthesized by reacting with an alkali metal salt of nitrogen-containing perfluoroalkanesulfonic acid having a forming ability or an alkali metal salt of imide containing nitrogen-containing perfluoroalkanesulfonic acid.

(In the formula, Rf ¹ , Rf ² and Rf ³ are the same as those described in the general formula (1), and M is an alkali metal or an alkaline earth metal corresponding to a monovalent group. [C] ⁺ is An onium cation and X is a halogen atom)

  In this case, the solvent used is appropriately selected from benzene, toluene, THF, DMF, diethyl ether, acetonitrile, dichloroethane, dichloromethane, chloroform, and other organic solvents or water. The reaction temperature is usually selected from the range of -20 ° C to the reflux temperature of the solvent, preferably -10 ° C to 30 ° C. Although the time required for the reaction varies depending on the reaction temperature and the amount of preparation, it is usually appropriately selected within the range of 10 minutes to 5 hours, preferably 20 minutes to 1 hour. The by-product metal halide can be easily removed by washing with distilled water.

  Tables 1 and 2 show melting points of typical compounds of the novel onium salts represented by the general formulas (2) to (5) according to the present invention.

The melting points of the novel 1,3-dialkylimidazolium salts (A to E) are all 100 ° C. or less, and are within the melting point range required for the ionic liquid. Even with the same 1-butyl-3-methylimidazolium homologue, the melting point is 54-55 ° C. in the case of perfluoro [2- (N, N-dimethylamino) ethanesulfonium] (compound C) due to the difference in counter anion. Perfluoro (1,3-dimethylaminomorpholinomethanesulfonium) (compound D) is a jelly-like compound at room temperature, and trifluoromethanesulfonyl perfluoro (morpholinomethanetansulfonyl) imidium (compound E) is a liquid compound at room temperature. , Showing different melting points. These are soluble in acetone and alcohol, but are insoluble or hardly soluble in water, and can be expected as synthetic solvents and catalysts or electrochemical applications as ionic liquids.

  The melting points of the new fourth organic onium (ammonium and phosphonium) salts (F to J) are all high melting points (200 ° C. or higher) except in the case of Compound F. Even when the same perfluoromorpholinomethanesulfonium is used as the counter anion, the tetraalkylammonium salt shows a relatively low melting point (72-73 ° C.) when the alkyl group is a tetrabutyl group (compound F). In the case of (Compound G), the melting point is as high as 233-234 ° C. Although these are soluble in acetone and alcohol, they are insoluble or hardly soluble in water, and can be expected to be applied to synthetic solvents and catalysts used in the field of organic chemistry, and supporting electrolytes in the field of electrochemistry.

  EXAMPLES Next, although an Example demonstrates this invention in detail, this invention is not controlled at all by these examples.

Example 1
Synthesis of tetraethylammonium perfluoro (morpholinomethanesulfonate) 1) Perfluoro [N- (methyl iodide) morpholine] used as a raw material for the synthesis of perfluoro (sodium morpholinomethanesulfonate ) was obtained by electrolytic fluorination of methyl morpholinoacetate. The resulting crude perfluoro (morpholinoacetic acid fluoride) was synthesized by reaction with lithium iodide.
A 200 ml eggplant flask is charged with a mixed solvent (15 ml water and 5 ml acetonitrile), dithionite (7.1 g), sodium bicarbonate (3.40 g), and then 12.6 g of fluorocarbon {into this Perfluoro [N- (methyl iodide) morpholine] containing 8.1 g} was added dropwise, and the reaction was performed at 55 ° C. for 10 hours with magnetic stirring. After the reaction, a white scaly solid was separated, and then the solvent was removed with a rotary evaporator. The reaction product was evaporated to dryness to obtain a white solid (15.3 g). This was extracted with ethyl acetate, and the solvent was removed to obtain a cream colored solid (8.0 g). This was dissolved again in 40 ml of ethyl acetate, washed twice with 6 ml of brine (10%), and the ethyl acetate was removed and dried to obtain 6.14 g of a white solid. When this compound was analyzed by ¹⁹ F-NMR, most of the compound was perfluoro (sodium morpholinomethanesulfinate), and in addition, a small amount of perfluoro (sodium morpholinomethanesulfonate) was mixed (mixing ratio; 96: 4) Was doing.
Next, perfluoro (sodium morpholinomethanesulfinate) obtained by the above reaction was converted to perfluoro (sodium morpholinomethanesulfonate) by oxidation with hydrogen peroxide.
Crude perfluoro (sodium morpholinomethanesulfinate) (6.14 g), 15 ml of 30% hydrogen peroxide and 1 ml of acetic acid were charged into a 100 ml eggplant flask and reacted at 76-103 ° C. for 7 hours. The reaction was transferred to a beaker and evaporated to dryness on a hot plate, yielding 6.10 g of a white solid. When this compound was analyzed by ¹⁹ F-NMR, perfluoro (sodium morpholinomethanesulfinate) was completely oxidized to perfluoro (sodium morpholinomethanesulfonate).
Perfluoro (sodium morpholinomethanesulfinate) and perfluoro (sodium morpholinomethanesulfonate) are novel compounds not described in the literature. The ¹⁹ F-NMR data are as follows.

ケミカルシフト(ppm：外部標準CF ₃ C(O)OH基準／溶媒：CD ₃ C(O)CD ₃ )
(1) -7.5(s)
(2) -11.5(triplet)
(3) -21.5(quintet)

カップリングコンスタント(Hz)
(2)−(3)＝14.1

ペルフルオロ(モルホリホリノメタンスルフィン酸ナトリウム)の¹⁹F-NMRデータは次の通リである。

Chemical shift (ppm: external standard CF ₃ C (O) OH standard / solvent: CD ₃ C (O) CD ₃ )
(1) -7.5 (s)
(2) -11.5 (triplet)
(3) -21.5 (quintet)

Coupling constant (Hz)
(2)-(3) = 14.1

The ¹⁹ F-NMR data of perfluoro (sodium morpholinomethanesulfinate) are as follows.

ケミカルシフト(ppm：外部標準CF ₃ C(O)OH基準／溶媒：CD ₃ C(O)CD ₃ )
(1) -7.5(s)
(2) -11.5(triplet)
(3) -21.5(quintet)

カップリングコンスタント(Hz)
(2)−(3)＝14.1

Chemical shift (ppm: external standard CF ₃ C (O) OH standard / solvent: CD ₃ C (O) CD ₃ )
(1) -7.5 (s)
(2) -11.5 (triplet)
(3) -21.5 (quintet)

Coupling constant (Hz)
(2)-(3) = 14.1

2) Synthesis of tetraethylammonium perfluoro (morpholinomethanesulfonate ) 0.5 g (1.3 mmol) of perfluoro (sodium morpholinomethanesulfonate), 0.22 g (1.3 mmol) of tetraethylammonium chloride and 7 ml of distilled water were mixed and stirred overnight at room temperature. . After the reaction, it was dissolved in 50 ml of methylene chloride, the organic layer was separated, washed twice with 20 ml of ion-exchanged water, and dried over magnesium sulfate. Next, the solvent was removed and the residue was dried with a vacuum line to obtain 0.27 g of a white powder. ^{According to 19} F-NMR analysis, this was tetraethylammonium perfluoro (morpholinomethanesulfonate), which was a solid having a melting point of 233-234 ° C. (yield 39%).
The ¹⁹ F-NMR spectrum data of tetraethylammonium perfluoro (morpholinomethanesulfonate) is shown below.

ケミカルシフト(ppm：外部標準CF₃C(O)OH基準／溶媒：CD₃C(O)CD₃)
(1) -8.5(s)
(2) -12.4(triplet)
(3) -6.5(quintet)

カップリングコンスタント(Hz)
(2)−(3)＝17-20

Chemical shift (ppm: external standard CF ₃ C (O) OH standard / solvent: CD ₃ C (O) CD ₃ )
(1) -8.5 (s)
(2) -12.4 (triplet)
(3) -6.5 (quintet)

Coupling constant (Hz)
(2)-(3) = 17-20

Example 2
Synthesis of tetrabutylammonium perfluoro (morpholinomethanesulfonate) Tetrabutylammonium perfluoro (morpholinomethanesulfonate) was reacted in the same manner as in Example 1 except that tetrabutylammonium bromide was used instead of tetraethylammonium chloride. (Yield 74%). Tetrabutylammonium perfluoro (morpholinomethanesulfonate) was a solid with a melting point of 72-73 ° C.
The ¹⁹ F-NMR spectrum data of tetrabutylammonium perfluoro (morpholinomethanesulfonate) is shown below.

ケミカルシフト(ppm：外部標準CF₃C(O)OH基準／溶媒：CD₃C(O)CD₃)
(1) -8.4(s)
(2) -12.3(triplet)
(3) -6.3(quintet)

カップリングコンスタント(Hz)
(2)−(3)＝17-20

Chemical shift (ppm: external standard CF ₃ C (O) OH standard / solvent: CD ₃ C (O) CD ₃ )
(1) -8.4 (s)
(2) -12.3 (triplet)
(3) -6.3 (quintet)

Coupling constant (Hz)
(2)-(3) = 17-20

Example 3
Synthesis of 1-ethyl-3-methylimidazolium perfluoro (morpholinomethanesulfonate) By reacting 1-ethyl-3-methylimidazolium bromide with perfluoro (sodium morpholinomethanesulfonate) in the same manner as in Example 1. 1-ethyl-3-methylimidazolium perfluoro (morpholinomethanesulfonate) was obtained (41% yield).
1-Ethyl-3-methylimidazolium perfluoro (morpholinomethanesulfonate) was a solid with a melting point of 93-94 ° C.
The ¹⁹ F-NMR spectrum data of 1-ethyl-3-methylimidazolium perfluoro (morpholinomethanesulfonate) obtained below is shown.

¹⁹ F-NMR data

ケミカルシフト(ppm：外部標準CF₃C(O)OH基準／溶媒：CD₃C(O)CD₃)
(1) -8.4(s)
(2) -12.4(triplet)
(3) -6.5(quintet)

カップリングコンスタント(Hz)
(2)−(3)＝17

Chemical shift (ppm: external standard CF ₃ C (O) OH standard / solvent: CD ₃ C (O) CD ₃ )
(1) -8.4 (s)
(2) -12.4 (triplet)
(3) -6.5 (quintet)

Coupling constant (Hz)
(2)-(3) = 17

Example 4
Synthesis of tetraethylammonium perfluoro (N, N-dimethylaminomethanesulfonate) Example 1 was used except that perfluoro (potassium N, N-dimethylaminomethanesulfonate) was used instead of perfluoro (sodium morpholinomethanesulfonate). Reaction was performed in the same manner to obtain tetraethylammonium perfluoro (N, N-dimethylaminomethanesulfonate) (yield 28%).
Tetraethylammonium perfluoro (N, N-dimethylaminomethanesulfonate) was a solid with a melting point of 219-223 ° C.
The ¹⁹ F-NMR spectrum data of tetraethylammonium perfluoro (N, N-dimethylaminomethanesulfonate) obtained below is shown.

¹⁹ F-NMR data

ケミカルシフト(ppm：外部標準CF₃C(O)OH基準／溶媒：CD₃C(O)CD₃)
(1) 26.5(triplet)
(2) -7.0(quintet)

カップリングコンスタント(Hz)
(1)−(2)＝14-17

Chemical shift (ppm: external standard CF ₃ C (O) OH standard / solvent: CD ₃ C (O) CD ₃ )
(1) 26.5 (triplet)
(2) -7.0 (quintet)

Coupling constant (Hz)
(1)-(2) = 14-17

Example 5
Synthesis of 1-ethyl-3-methylimidazolium perfluoro [2- (N, N-dimethylamino) ethanesulfonate) Perfluoro [2- (N, N-dimethylamino) instead of perfluoro (sodium morpholinomethanesulfonate) The reaction is carried out in the same manner as in Example 2 except that sodium ethanesulfonate] is used to obtain 1-ethyl-3-methylimidazolium perfluoro [2- (N, N-dimethylamino) ethanesulfonate). (55% yield).
1-ethyl-3-methylimidazolium perfluoro [2- (N, N-dimethylamino) ethanesulfonate) was a solid with a melting point of 61-62 ° C.
The ¹⁹ F-NMR spectrum data of 1-ethyl-3-methylimidazolium perfluoro [2- (N, N-dimethylamino) ethanesulfonate) is shown below.

¹⁹ F-NMR data

ケミカルシフト(ppm：外部標準CF₃C(O)OH基準／溶媒：CD₃C(O)CD₃)
(1) 25.9(triplet-triplet)
(2) -11.0(heptet)
(3) -36.5(heptet)

カップリングコンスタント(Hz)
(1)−(2)＝14-17
(1)−(3)＝8.5

Chemical shift (ppm: external standard CF ₃ C (O) OH standard / solvent: CD ₃ C (O) CD ₃ )
(1) 25.9 (triplet-triplet)
(2) -11.0 (heptet)
(3) -36.5 (heptet)

Coupling constant (Hz)
(1)-(2) = 14-17
(1)-(3) = 8.5

Example 6
Synthesis of 1 -butyl-3-methylimidazolium perfluoro [2- (N, N-dimethylamino) ethanesulfonate) 1-butyl-3-methylimidazolium bromide instead of 1-ethyl-3-methylimidazolium bromide Was used in the same manner as in Example 4 to obtain 1-butyl-3-methylimidazolium perfluoro [2- (N, N-dimethylamino) ethanesulfonate] (yield 57). %).
1-butyl-3-methylimidazolium perfluoro [2- (N, N-dimethylamino) ethanesulfonate) was a solid with a melting point of 54-55 ° C.
The ¹⁹ F-NMR spectrum data of 1-butyl-3-methylimidazolium perfluoro [2- (N, N-dimethylamino) ethanesulfonate) is shown below.

¹⁹ F-NMR data

ケミカルシフト(ppm：外部標準CF₃C(O)OH基準／溶媒：CD₃C(O)CD₃)
(1) 25.9(triplet-triplet)
(2) -11.0(heptet)
(3) -36.5(heptet)

カップリングコンスタント(Hz)
(1)−(2)＝14-17
(1)−(3)＝8.5

Chemical shift (ppm: external standard CF ₃ C (O) OH standard / solvent: CD ₃ C (O) CD ₃ )
(1) 25.9 (triplet-triplet)
(2) -11.0 (heptet)
(3) -36.5 (heptet)

Coupling constant (Hz)
(1)-(2) = 14-17
(1)-(3) = 8.5

Example 7
Synthesis of benzyl trimethylammonium perfluoro (morpholinomethanetansulfonate) The reaction was conducted in the same manner as in Example 1 except that benzyl trimethylammonium chloride was used instead of tetraethylammonium chloride, and benzyl trimethylammonium perfluoro ( Morpholinomethanetansulfonate) was obtained (yield 59%).
Benzyltrimethylammonium perfluoro (morpholinomethanetansulfonate) was a solid with a melting point of 160-161 ° C.
The ¹⁹ F-NMR spectrum data of benzyl-trimethylammonium perfluoro (morpholinomethanetansulfonate) is shown below.

¹⁹ F-NMR data

ケミカルシフト(ppm：外部標準CF₃C(O)OH基準／溶媒：CD₃C(O)CD₃)
(1) -8.4(s)
(2) -12.3(triplet)
(3) -6.4(quintet)

カップリングコンスタント(Hz)
(2)−(3)＝17-20

Chemical shift (ppm: external standard CF ₃ C (O) OH standard / solvent: CD ₃ C (O) CD ₃ )
(1) -8.4 (s)
(2) -12.3 (triplet)
(3) -6.4 (quintet)

Coupling constant (Hz)
(2)-(3) = 17-20

Example 8
Synthesis of 1-butyl-3-methylimidazolium perfluoro (1,6-dimethylmorpholinomethanetansulfonate) Perfluoro (1,6 -dimethyl) instead of sodium perfluoro [2- (N, N-dimethylamino) ethanesulfonate The reaction was carried out in the same manner as in Example 5 except that (morpholinomethanesulfonate potassium) was used to obtain 1-butyl-3-methylimidazolium perfluoro (1,6-dimethylmorpholinomethanetansulfonate) ( Yield 66%).
1-butyl-3-methylimidazolium perfluoro (1,6-dimethylmorpholinomethanetansulfonate) was a light yellow jelly-like compound at room temperature.
The ¹⁹ F-NMR spectrum data of 1-butyl-3-methylimidazolium perfluoro (1,6-dimethylmorpholinomethanetansulfonate) (Cis-isomer / Trans-isomer ratio = 1: 0.51) is shown below. .

¹⁹ F-NMR data

ケミカルシフト(ppm：外部標準CF₃C(O)OH基準／溶媒：CD₃C(O)CD₃)

Cis-体
(1) -2.6(multiplet)
(2) -49.4(multiplet)
(3) 1.4,-16.7 J(AB)=209Hz
(4) -5.7(multiplet)

Trans-体
(1) -2.2(multiplet)
(2) -44.9(multiplet)
(3) 5.1,-14.4 J(AB)=198Hz
(4) 1.8,-10.4 J(AB)=215Hz

Chemical shift (ppm: external standard CF ₃ C (O) OH standard / solvent: CD ₃ C (O) CD ₃ )

Cis-body
(1) -2.6 (multiplet)
(2) -49.4 (multiplet)
(3) 1.4, -16.7 J (AB) = 209Hz
(4) -5.7 (multiplet)

Trans-body
(1) -2.2 (multiplet)
(2) -44.9 (multiplet)
(3) 5.1, -14.4 J (AB) = 198Hz
(4) 1.8, -10.4 J (AB) = 215Hz

Example 9
Synthesis of 1-butyl-3-methylimidazolium trifluoromethanesulfonyl perfluoro (morpholinomethanetansulfonyl) imide Perfluoro [2- (N, N-dimethylamino) ethanesulfonate instead of sodium trifluoromethanesulfonyl perfluoro (morpholinome) The reaction was carried out in the same manner as in Example 5 except that tantansulfonyl) imide lithium salt was used to obtain 1-butyl-3-methylimidazolium trifluoromethanesulfonyl / perfluoro (morpholinomethanetansulfonyl) imide (yield). 84%).
1-butyl-3-methylimidazolium trifluoromethanesulfonyl perfluoro (morpholinomethanetansulfonyl) imide was a light yellow transparent liquid at room temperature.
The synthesis of trifluoromethanesulfonyl / perfluoro (morpholinomethanetansulfonyl) imide lithium salt was performed as follows.
Synthesis of trifluoromethanesulfonyl-perfluoro (morpholinomethanetansulfonyl) imide lithium salt In a two-necked flask (volume: 50 ml), 1.13 g (7.6 mmol) of trifluoromethanesulfonamide, 2.90 g (8.0 mmol) of perfluoromorpholinomethanesulfonic acid fluoride, and 20 ml of triethylamine was charged and magnetic stirring was performed at 70 ° C. for 20 hours. After the reaction, the volatile components are removed with a vacuum line, dissolved in 40 ml of methylene chloride, shaken with an equal volume of water to remove water-soluble components, and the methylene chloride layer is dried over anhydrous magnesium sulfate. Further, when the solvent was removed with a rotary evaporator, 3.66 g of a viscous liquid was obtained.
Subsequently, 10 ml of sulfuric acid was added and vacuum distillation was performed to obtain trifluoromethanesulfonyl perfluoro (morpholinomethanetansulfonyl) imide as a light yellow transparent liquid (1.77 g, boiling point: 65-69 ° C./65 mmHg). Yield: 47%).
The corresponding lithium salt was synthesized by dissolving 1.6 g (3.3 mmol) of imide in 3 ml of ether and adding equimolar lithium carbonate thereto. The crude product was evaporated to dryness, washed with methylene chloride, filtered and dried to produce a purified lithium salt (1.29 g, yield: 79%).

Below, ¹⁹ F- of trifluoromethanesulfonyl perfluoro (morpholinomethanetansulfonyl) imide lithium salt obtained as a novel compound, and 1-butyl-3-methylimidazolium trifluoromethanesulfonyl perfluoro (morpholinomethanetanesulfonyl) imide NMR spectrum data is shown.

¹⁹ F-NMR data

ケミカルシフト(ppm：外部標準CF₃C(O)OH基準／溶媒：CD₃C(O)CD₃)
(1) -8.7(s)
(2) -13.0(triplet)
(3) -7.1(quintet)
(4) -1.2(s)

カップリングコンスタント(Hz)
(2)−(3)＝17-20
¹⁹ F-NMRデータ

Chemical shift (ppm: external standard CF ₃ C (O) OH standard / solvent: CD ₃ C (O) CD ₃ )
(1) -8.7 (s)
(2) -13.0 (triplet)
(3) -7.1 (quintet)
(4) -1.2 (s)

Coupling constant (Hz)
(2)-(3) = 17-20
¹⁹ F-NMR data

ケミカルシフト(ppm：外部標準CF₃C(O)OH基準／溶媒：CD₃C(O)CD₃)
(1) -8.6(s)
(2) -12.9(triplet)
(3) -7.0(quintet)
(4) -1.2(s)

カップリングコンスタント(Hz)
(2)−(3)＝17-20

Chemical shift (ppm: external standard CF ₃ C (O) OH standard / solvent: CD ₃ C (O) CD ₃ )
(1) -8.6 (s)
(2) -12.9 (triplet)
(3) -7.0 (quintet)
(4) -1.2 (s)

Coupling constant (Hz)
(2)-(3) = 17-20

Example 10
Synthesis of benzyl triphenylphosphonium perfluoro (pyrrolidinomethanesulfonate) Benzyltriphenylphosphonium chloride is used in place of benzyltrimethylammonium chloride, and perfluoro (pyrrolidinomethane sulfonate potassium) is used in place of perfluoro (potassium morpholinomethanetansulfonate). The reaction was conducted in the same manner as in Example 8 except that 2 days was employed as the reaction time, and benzyl triphenylphosphonium perfluoro (pyrrolidinomethanesulfonate) was used as the corresponding onium salt. (Yield 79%)
Benzyl triphenylphosphonium perfluoro (pyrrolidinomethanesulfonate) was a solid with a melting point of 149-151 ° C.
The ¹⁹ F-NMR spectrum data of the newly obtained benzyl triphenylphosphonium perfluoro (pyrrolidinomethanesulfonate) is shown below.

¹⁹ F-NMR data

ケミカルシフト(ppm：外部標準CF₃C(O)OH基準／溶媒：CD₃C(O)CD₃)
(1) -55.5(s)
(2) -12.3(triplet)
(3) -7.4(quintet)

カップリングコンスタント(Hz)
(2)−(3)＝11-14

Chemical shift (ppm: external standard CF ₃ C (O) OH standard / solvent: CD ₃ C (O) CD ₃ )
(1) -55.5 (s)
(2) -12.3 (triplet)
(3) -7.4 (quintet)

Coupling constant (Hz)
(2)-(3) = 11-14

Claims (4)

General formula (2)

(In the formula, R ^{1 to} R ⁵ are each independently hydrogen or an alkyl group, alkenyl group, aryl group or aralkyl group having 30 or less carbon atoms , and these groups may be branched . R _f ¹ And R _f ² are the same or different perfluoroalkyl groups having 1 to 5 carbon atoms, both of which are bonded directly or through an oxygen atom or a nitrogen atom, and complex together with the nitrogen atom to which they are bonded. A nitrogen-containing perfluoroalkane sulfonate represented by the following formula: R _f ³ represents a branched or linear perfluoroalkylene group having 1 to 4 carbon atoms . General formula (3)

(R ^{1 to} R ⁴ in the formula are each independently an alkyl group, alkenyl group, aryl group or aralkyl group having 30 or less carbon atoms , and these groups may be branched . R _f ¹ and R _f ² Are the same or different perfluoroalkyl groups having 1 to 5 carbon atoms, which are bonded directly or through an oxygen atom or a nitrogen atom to form a heterocyclic ring together with the nitrogen atom to which they are bonded. R _f ³ represents a novel nitrogen-containing perfluoroalkanesulfonate salt represented by a branched or linear perfluoroalkylene group having 1 to 4 carbon atoms . General formula (4)

(R ^{1 to} R ⁴ in the formula are each independently an alkyl group, alkenyl group, aryl group or aralkyl group having 30 or less carbon atoms , and these groups may be branched . R _f ¹ and R _f ² Are the same or different perfluoroalkyl groups having 1 to 5 carbon atoms, which are bonded directly or through an oxygen atom or a nitrogen atom to form a heterocyclic ring together with the nitrogen atom to which they are bonded. R _f ³ represents a branched or straight-chain perfluoroalkylene group having 1 to 4 carbon atoms ). General formula (5)

(In the formula, R ^{1 to} R ⁵ are each independently hydrogen or an alkyl group, alkenyl group, aryl group or aralkyl group having 30 or less carbon atoms, and these groups may be branched. R _f ¹ And R _f ² are the same or different perfluoroalkyl groups having 1 to 5 carbon atoms, both of which are bonded directly or through an oxygen atom or a nitrogen atom, and complex together with the nitrogen atom to which they are bonded. R _f ³ represents a branched or linear perfluoroalkylene group having 1 to ⁴ carbon atoms, R _f ⁴ represents a linear perfluoroalkyl group having 1 to ⁴ carbon atoms, Or a nitrogen-containing perfluoroalkanesulfonic acid salt represented by the same formula as the nitrogen-containing perfluoroalkane group that is the other component of the imide salt.