JP5544892B2 - Process for producing 2-cyano-1,3-diketonate salt and ionic liquid - Google Patents

Description

  The present invention relates to a method for producing a 2-cyano-1,3-diketonate salt and an ionic liquid using the same.

As a method for producing 2-cyano-1,3-diketonate salt and its precursor 2-cyano-1,3-diketone, Non-Patent Document 1 discloses a production method using dicyan as a reagent for introducing a cyano group. ing. However, dicyan has a problem of extremely high toxicity. As a safer production method, Non-Patent Document 2 discloses a production method by reaction of 1,3-diketone and chlorosulfonyl isocyanate. However, although chlorosulfonyl isocyanate is less toxic than dicyan, it is known to strongly irritate the skin, eyes and mucous membranes and cause inflammation and chemical injury. Further, there is a risk of injuring the lungs when inhaled, and a safer manufacturing method is required. Furthermore, the production method of Non-Patent Document 2 discloses that the reaction does not proceed with a 1,3-diketone having a CF ₃ group.

The ionic liquid is generally composed of a combination of a cation such as imidazolinium and an anion such as Br ⁻ , Cl ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , (CF ₃ SO ₂ ) ₂ N ⁻ , and flame retardancy. In order to show non-volatility, high ionic conductivity, and excellent thermal stability, application to electrolytes for batteries and capacitors, solvents with high environmental compatibility (green solvents), and the like have been widely studied.

  One of the characteristics of ionic liquids is diversity. The more diverse the ionic liquid structure, the more optimal ionic liquid can be selected for the application. Developing new ionic liquids and supplying various ionic liquids will lead to expanded applications of ionic liquids.

Inorganic Chemistry, Vol. 30, pp 1943-1949, 1991 Polyhedron, Vol. 20, pp 3113-3117, 2001

The present invention has been made in view of the above circumstances, and provides a process for producing a 2-cyano-1,3-diketonate salt that is safer than before and also has a 2-cyano-1,3 having a CF ₃ group. -The first object is to enable the production of diketonate salts. A second object is to provide a novel ionic liquid.

In order to solve the above-mentioned problems, the present inventor has conducted extensive research and made the following invention.
The present invention has the following chemical formula (1)

（式中、Ｒ_１、Ｒ_２は、水素原子、炭素数が１０以下のアルキル基、ハロゲン化アルキル基、アリール基、又は複素環基を示し、ＭはＬｉ、Ｎａ、Ｋ、ＮＨ_４、Ａｇのいずれかを示す。）
で示される２−シアノ−１，３−ジケトネート塩の製造法であって、アセトニトリルと下記化学式（２）

(In the formula, R ₁ and R ₂ represent a hydrogen atom, an alkyl group having 10 or less carbon atoms, a halogenated alkyl group, an aryl group, or a heterocyclic group, and M represents Li, Na, K, NH ₄ , Ag. Indicates one of these.)
A process for producing a 2-cyano-1,3-diketonate salt represented by formula (2): acetonitrile and the following chemical formula (2)

（式中、Ｒ_１は、水素原子、炭素数が１０以下のアルキル基、ハロゲン化アルキル基、アリール基、又は複素環基を示し、Ｒ_３は、炭素数が６以下のアルキル基を示す。）
で示されるカルボン酸エステルと、下記化学式（３）

(In the formula, R ₁ represents a hydrogen atom, an alkyl group having 10 or less carbon atoms, a halogenated alkyl group, an aryl group, or a heterocyclic group, and R ₃ represents an alkyl group having 6 or less carbon atoms. )
A carboxylic acid ester represented by the following chemical formula (3)

（式中、Ｒ_４は、炭素数が６以下のアルキル基を示し、Ｍ′はＬｉ、Ｎａ、又はＫを示す。）
で示されるアルカリ金属アルコキシドとを反応させ、下記化学式（４）

(In the formula, R ₄ represents an alkyl group having 6 or less carbon atoms, and M ′ represents Li, Na, or K.)
Is reacted with an alkali metal alkoxide represented by the following chemical formula (4):

（式中、Ｒ_１は、水素原子、炭素数が１０以下のアルキル基、ハロゲン化アルキル基、アリール基、又は複素環基を示し、Ｍ′はＬｉ、Ｎａ、又はＫを示す。）
で示されるα−シアノケトンアルカリ金属塩を製造する第一工程と、上記化学式（４）で示されるα−シアノケトンアルカリ金属塩と、下記化学式（５）

(In the formula, R ₁ represents a hydrogen atom, an alkyl group having 10 or less carbon atoms, a halogenated alkyl group, an aryl group, or a heterocyclic group, and M ′ represents Li, Na, or K.)
A first step of producing an α-cyanoketone alkali metal salt represented by the formula: α-cyanoketone alkali metal salt represented by the chemical formula (4);

（式中、Ｒ_２は、水素原子、炭素数が１０以下のアルキル基、ハロゲン化アルキル基、アリール基、又は複素環基を示し、ＸはＲ_２ＣＯＯ基、塩素原子、又は臭素原子を示す。）
で示されるカルボン酸無水物又はカルボン酸ハロゲン化物とを反応させ、下記化学式（６）

(In the formula, R ₂ represents a hydrogen atom, an alkyl group having 10 or less carbon atoms, a halogenated alkyl group, an aryl group, or a heterocyclic group, and X represents an R ₂ COO group, a chlorine atom, or a bromine atom. .)
Is reacted with a carboxylic acid anhydride or a carboxylic acid halide represented by the following chemical formula (6):

（式中、Ｒ_１、Ｒ_２は、水素原子、炭素数が１０以下のアルキル基、ハロゲン化アルキル基、アリール基、又は複素環基を示す。）
で示される２−シアノ−１，３−ジケトンを製造する第二工程と、上記化学式（６）で示される２−シアノ−１，３−ジケトンとアルカリ金属塩、アルカリ金属、アンモニア又は銀塩とを反応させる第三工程とから成ることを特徴とする。
また、本発明は、上記化学式（１）で示される２−シアノ−１，３−ジケトネート塩の製造法であって、アセトニトリルと上記化学式（２）で示されるカルボン酸エステルと、上記化学式（３）で示されるアルカリ金属アルコキシドとを反応させ、上記化学式（４）で示されるα−シアノケトンアルカリ金属塩を製造する第一工程と、上記第二工程および上記第三工程に代えて、第一の塩基の存在下、上記化学式（４）で示されるα−シアノケトンアルカリ金属塩と上記化学式（５）で示されるカルボン酸無水物又はカルボン酸ハロゲン化物とを反応させ下記化学式（７）

(In the formula, R ₁ and R ₂ represent a hydrogen atom, an alkyl group having 10 or less carbon atoms, a halogenated alkyl group, an aryl group, or a heterocyclic group.)
A second step of producing a 2-cyano-1,3-diketone represented by formula (2), a 2-cyano-1,3-diketone represented by the chemical formula (6) and an alkali metal salt, an alkali metal, ammonia or a silver salt; And a third step of reacting.
The present invention also provides a method for producing a 2-cyano-1,3-diketonate salt represented by the chemical formula (1), comprising acetonitrile, a carboxylic acid ester represented by the chemical formula (2), and the chemical formula (3). The first step of producing the α-cyanoketone alkali metal salt represented by the chemical formula (4) by reacting with the alkali metal alkoxide represented by In the presence of the base, the α-cyanoketone alkali metal salt represented by the chemical formula (4) is reacted with the carboxylic acid anhydride or carboxylic acid halide represented by the chemical formula (5) to obtain the following chemical formula (7).

（式中、Ｒ_１、Ｒ_２は、水素原子、炭素数が１０以下のアルキル基、ハロゲン化アルキル基、アリール基、又は複素環基を示し、Ｂは第一の塩基を示す。）
で示される塩を製造する第四工程と、上記化学式（７）で示される塩と上記第一の塩基よりも共役酸のｐＫａが大きい第二の塩基又はアルカリ金属とを反応させる第五工程から成ることを特徴とする。ここで、上記第一の塩基としてはトリエチルアミンが好ましい。また、上記第二の塩基としては水素化ナトリウムが好ましい。

(Wherein R ₁ and R ₂ represent a hydrogen atom, an alkyl group having 10 or less carbon atoms, a halogenated alkyl group, an aryl group, or a heterocyclic group, and B represents a first base.)
From the fourth step of producing the salt represented by formula (5) and the fifth step of reacting the salt represented by the chemical formula (7) with a second base or alkali metal having a pKa of a conjugate acid larger than that of the first base. It is characterized by comprising. Here, triethylamine is preferred as the first base. The second base is preferably sodium hydride.

  The present invention also provides a method for producing a 2-cyano-1,3-diketonate salt represented by the chemical formula (1), comprising acetonitrile, a carboxylic acid ester represented by the chemical formula (2), and the chemical formula (3). In the first step of producing an α-cyanoketone alkali metal salt represented by the above chemical formula (4) by reacting with an alkali metal alkoxide represented by formula (4), LiH, Sixth step of reacting the α-cyanoketone alkali metal salt represented by the chemical formula (4) with the carboxylic acid anhydride or carboxylic acid halide represented by the chemical formula (5) in the presence of either NaH or KH. It is characterized by having.

Furthermore, the present invention relates to an ionic liquid comprising a cation component and an anion component, wherein the cation component is an organic cation, and the anion component relates to an ionic liquid having a chemical structure represented by the following chemical formula (8). However, in formula, R < ₁ >, R < ₂ > shows a hydrogen atom, a C10 or less alkyl group, a halogenated alkyl group, an aryl group, or a heterocyclic group. A ring may be formed between R ₁ and R ₂ .

また、上記化学式（８）中、Ｒ_１、Ｒ_２は、ＣＨ_３、ＣＨ_２ＣＨ_３、ＣＨ_２ＣＨ_２ＣＨ_３、Ｃ（ＣＨ_３）_３、ＣＦ_３、ＣＦ_２ＣＦ_３、ＣＦ_２ＣＦ_２ＣＦ_３のいずれかであることが好ましい。

In the chemical formula (8), R ₁ and R ₂ are CH ₃ , CH ₂ CH ₃ , CH ₂ CH ₂ CH ₃ , C (CH ₃ ) ₃ , CF ₃ , CF ₂ CF ₃ , CF ₂ CF _2. it is preferably any one of CF _3.

  Furthermore, the anion component is preferably a 3-cyano-1,1,1,5,5,5-hexafluoroacetylacetonate anion represented by the following chemical formula (9).

また、上記アニオン成分は、下記化学式（１０）で示される３−シアノ−１，１，１−トリフルオロアセチルアセトネートアニオンが好ましい。

The anion component is preferably a 3-cyano-1,1,1-trifluoroacetylacetonate anion represented by the following chemical formula (10).

さらに、上記カチオン成分は、下記化学式（１１）で示される群から選ばれる少なくとも１種であることが好ましい。但し、式中、Ｒ_１〜Ｒ_４は、水素原子、炭素数が２０以下のアルキル基、アルコキシアルキル基、トリアルキルシリルアルキル基、アルケニル基、アルキニル基、アリール基、又は複素環基を示し、Ｒ´_１〜Ｒ´_１０は水素原子、炭素数が１０以下のアルキル基、アルコキシアルキル基、トリアルキルシリルアルキル基、アルケニル基、アルキニル基、アリール基、又は複素環基を示す。

Furthermore, the cation component is preferably at least one selected from the group represented by the following chemical formula (11). In the formula, R ₁ to R ₄ is a hydrogen atom, an alkyl group having 20 or less carbon atoms, an alkoxyalkyl group, a trialkylsilyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, R ′ _{1 to} R ′ ₁₀ represent a hydrogen atom, an alkyl group having 10 or less carbon atoms, an alkoxyalkyl group, a trialkylsilylalkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group.

また、本発明のイオン液体は、下記化学式（１２）で示される構造を有することが好ましい。

Moreover, it is preferable that the ionic liquid of this invention has a structure shown by following Chemical formula (12).

さらに、本発明のイオン液体は、下記化学式（１３）で示される構造を有することが好ましい。

Furthermore, the ionic liquid of the present invention preferably has a structure represented by the following chemical formula (13).

また、本発明のイオン液体は、下記化学式（１４）で示される構造を有することが好ましい。

Moreover, it is preferable that the ionic liquid of this invention has a structure shown by following Chemical formula (14).

さらに、本発明のイオン液体は、下記化学式（１５）で示される構造を有することが好ましい。

Furthermore, the ionic liquid of the present invention preferably has a structure represented by the following chemical formula (15).

The method for producing a 2-cyano-1,3-diketonate salt of the present invention can be produced more safely than conventional methods because acetonitrile with low toxicity is used as a reagent for introducing a cyano group. Further, it is possible to produce a 2-cyano-1,3-diketonate salt having a CF ₃ group, which has been difficult by the conventional synthesis method. Furthermore, a novel ionic liquid can be provided using 2-cyano-1,3-diketonate salt as a raw material.

Hereinafter, the present invention will be described in more detail. However, the present invention is not limited to this embodiment and examples.
Production of 2-cyano-1,3-diketonate salt The production method of 2-cyano-1,3-diketonate salt of the present invention comprises 2-cyano-1,3-diketone (chemical formula ( 6)) is classified into three production methods: a stable case and an unstable case, and a case where a 2-cyano-1,3-diketonate alkali metal salt is produced.
<Production method 1: When 2-cyano-1,3-diketone is stable>
Manufacturing method 1 consists of three steps. The first step is represented by the following reaction formula (1).

（式中、Ｒ_１は、水素原子、炭素数が１０以下のアルキル基、ハロゲン化アルキル基、アリール基、又は複素環基を示し、Ｒ_３、Ｒ_４は、炭素数が６以下のアルキル基を示す。また、Ｍ′はＬｉ、Ｎａ、又はＫを示す。）
Ｒ_１としては水素原子、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、フェニル基、２−フラニル基、２−チエニル基が好ましい。Ｒ_３とＲ_４は同一でも異なっていてもよく、メチル基又はエチル基が好ましい。

(In the formula, R ₁ represents a hydrogen atom, an alkyl group having 10 or less carbon atoms, a halogenated alkyl group, an aryl group, or a heterocyclic group, and R ₃ and R ₄ are alkyl groups having 6 or less carbon atoms. M ′ represents Li, Na, or K.)
R ₁ is a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, phenyl group, 2-furanyl group, 2-thienyl. Groups are preferred. R ₃ and R ₄ may be the same or different and are preferably a methyl group or an ethyl group.

  It is preferable to use 1 to 10 mol of acetonitrile and 1 to 2 mol of the carboxylic acid ester represented by the chemical formula (2) with respect to 1 mol of the alkali metal alkoxide represented by the chemical formula (3).

  As the solvent used in the first step, alcohols such as methanol and ethanol, and ethers such as diethyl ether and THF can be used. Moreover, the raw material and the solvent can be used together by using acetonitrile in excess. It is preferable to use 1 to 10 mL of the solvent with respect to 1 g of the alkali metal alkoxide represented by the chemical formula (3).

  The reaction temperature in the first step is preferably 0 ° C to 100 ° C. The reaction time is preferably 30 minutes to 24 hours.

  The reaction mixture is concentrated, and the precipitated solid is separated by filtration to obtain an α-cyanoketone alkali metal salt represented by the chemical formula (4). Further, it can be purified by recrystallization or column chromatography.

  The second step is represented by the following reaction formula (2).

（式中、Ｒ_１、Ｒ_２は、水素原子、炭素数が１０以下のアルキル基、ハロゲン化アルキル基、アリール基、又は複素環基を示す。また、Ｍ′はＬｉ、Ｎａ、又はＫを示し、ＸはＲ_２ＣＯＯ基、塩素原子、又は臭素原子を示す。）
Ｒ_２としては水素原子、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、フェニル基、２−フラニル基、２−チエニル基が好ましく、Ｒ_１とＲ_２は同一でも異なっていてもよい。

(Wherein R ₁ and R ₂ represent a hydrogen atom, an alkyl group having 10 or less carbon atoms, a halogenated alkyl group, an aryl group, or a heterocyclic group. M ′ represents Li, Na, or K. X represents an R ₂ COO group, a chlorine atom, or a bromine atom.)
R ₂ is hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, phenyl group, 2-furanyl group, 2-thienyl. A group is preferred, and R ₁ and R ₂ may be the same or different.

  It is preferable to use 0.8 to 1.2 mol of the carboxylic acid anhydride or carboxylic acid halide represented by the chemical formula (5) with respect to 1 mol of the α-cyanoketone alkali metal salt represented by the chemical formula (4). .

  As the solvent used in the second step, ethers such as diethyl ether and THF can be used. It is preferable to use 1 to 10 mL of the solvent with respect to 1 g of the α-cyanoketone alkali metal salt represented by the chemical formula (4).

  The reaction temperature in the second step is preferably -20 ° C to 100 ° C. The reaction time is preferably 1 hour to 48 hours.

  The 2-cyano-1,3-diketone represented by the chemical formula (6) can be isolated by distillation and / or column chromatography.

  The third step is represented by the following reaction formula (3).

（式中、Ｒ_１、Ｒ_２は、水素原子、炭素数が１０以下のアルキル基、ハロゲン化アルキル基、アリール基、又は複素環基を示す。また、ＭはＬｉ、Ｎａ、Ｋ、ＮＨ_４、Ａｇのいずれかであり、ＭＡはＬｉＯＨ、ＮａＯＨ、ＫＯＨ、ＬｉＨ、ＮａＨ、ＫＨ、Ｌｉ、Ｎａ、Ｋ、ＬｉＮＨ_２、ＮａＮＨ_２、ＫＮＨ_２、リチウムジイソプロピルアミド、ＮＨ_３、硝酸銀、又は酢酸銀のいずれかを示す。）
前記化学式（６）で示される２−シアノ−１，３−ジケトン１モルに対し、前記反応式（３）中のＭＡは０．８〜１．２モル用いることが好ましい。
第三工程に使用される溶媒としては、ジエチルエーテル、ＴＨＦ等のエーテル類を用いることができる。溶媒は、前記化学式（６）で示される２−シアノ−１，３−ジケトン１ｇに対し、１〜１０ｍＬ用いることが好ましい。

(In the formula, R ₁ and R ₂ represent a hydrogen atom, an alkyl group having 10 or less carbon atoms, a halogenated alkyl group, an aryl group, or a heterocyclic group. M represents Li, Na, K, NH _4. is either Ag, MA is LiOH, NaOH, KOH, LiH, NaH, KH, Li, Na, K, LiNH 2, NaNH 2, KNH 2, lithium diisopropylamide, NH _3, silver nitrate, or silver acetate Indicates either.)
It is preferable to use 0.8 to 1.2 mol of MA in the reaction formula (3) with respect to 1 mol of 2-cyano-1,3-diketone represented by the chemical formula (6).
As the solvent used in the third step, ethers such as diethyl ether and THF can be used. It is preferable to use 1 to 10 mL of the solvent with respect to 1 g of 2-cyano-1,3-diketone represented by the chemical formula (6).

  The reaction temperature in the third step is preferably -20 ° C to 100 ° C. The reaction time is preferably 1 hour to 48 hours.

  The 2-cyano-1,3-diketonate salt represented by the chemical formula (1) can be isolated by recrystallization and / or column chromatography.

<Production method 2: When 2-cyano-1,3-diketone is unstable>
The 2-cyano-1,3-diketone represented by the chemical formula (6) is unstable depending on the substituent as in the case where R ₁ or R ₂ is a trifluoromethyl group, and decomposes during production. In such a case, production method 2 is suitable. Production method 2 can also be applied when 2-cyano-1,3-diketone is stable.

The production method 2 includes three steps, and the first step is represented by the reaction formula (1) as in the production method 1. R ₁ is a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, trifluoromethyl group, pentafluoroethyl group, par Fluoro-n-propyl group, perfluoroisopropyl group, perfluoro-n-butyl group, perfluoroisobutyl group, perfluoro-sec-butyl group, perfluoro-tert-butyl group, phenyl group, 2-furanyl group, 2 It can carry out similarly to the 1st process of the manufacturing method 1 except a -thienyl group being preferable.
The second step is represented by the following reaction formula (4).

（式中、Ｒ_１、Ｒ_２は、水素原子、炭素数が１０以下のアルキル基、ハロゲン化アルキル基、アリール基、又は複素環基を示す。また、Ｍ′はＬｉ、Ｎａ、又はＫを示し、ＸはＲ_２ＣＯＯ基、塩素原子、又は臭素原子を示し、Ｂは塩基を示す。）
Ｒ_１、Ｒ_２としては水素原子、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、トリフルオロメチル基、ペンタフルオロエチル基、パーフルオロ−ｎ−プロピル基、パーフルオロイソプロピル基、パーフルオロ−ｎ−ブチル基、パーフルオロイソブチル基、パーフルオロ−ｓｅｃ−ブチル基、パーフルオロ−ｔｅｒｔ−ブチル基、フェニル基、２−フラニル基、２−チエニル基が好ましく、Ｒ_１とＲ_２は同一でも異なっていてもよい。Ｂとしては共役酸のｐＫａが５以上である塩基が好ましく９以上である塩基が特に好ましい。具体的には脂肪族３級アミン、芳香族３級アミン、ピリジン、Ｎ−アルキルイミダゾール、４−ジメチルアミノピリジン、１，８−ジアザビシクロ［５．４．０］ウンデカ−７−エン、１，５−ジアザビシクロ［４．３．０］ノナ−５−エンが好ましく用いられるが、経済性、取り扱いの容易さ、次の工程後の分離のしやすさを考慮するとトリエチルアミンが特に好ましい。塩基Ｂの共役酸のｐＫａとはＢＨ^＋の酸解離定数Ｋａの負の常用対数のことであり、下記〔式１〕で示される。
［式１］

（式中、［Ｂ］、［Ｈ^＋］、［ＢＨ^＋］はそれぞれＢ、Ｈ^＋、ＢＨ^＋のモル濃度を示す。ｐＫａは２５℃に於ける水中での値を使用する。）
前記化学式（４）で示されるα−シアノケトンアルカリ金属塩１モルに対し、前記化学式（５）で示されるカルボン酸無水物又はカルボン酸ハロゲン化物及び塩基Ｂはそれぞれ０．８〜１．２モル用いることが好ましい。

(Wherein R ₁ and R ₂ represent a hydrogen atom, an alkyl group having 10 or less carbon atoms, a halogenated alkyl group, an aryl group, or a heterocyclic group. M ′ represents Li, Na, or K. X represents an R ₂ COO group, a chlorine atom, or a bromine atom, and B represents a base.)
R ₁ and R ₂ are hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, trifluoromethyl group, pentafluoroethyl. Group, perfluoro-n-propyl group, perfluoroisopropyl group, perfluoro-n-butyl group, perfluoroisobutyl group, perfluoro-sec-butyl group, perfluoro-tert-butyl group, phenyl group, 2-furanyl Group, 2-thienyl group is preferable, and R ₁ and R ₂ may be the same or different. As B, a base having a pKa of a conjugate acid of 5 or more is preferred, and a base of 9 or more is particularly preferred. Specifically, aliphatic tertiary amine, aromatic tertiary amine, pyridine, N-alkylimidazole, 4-dimethylaminopyridine, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,5 -Diazabicyclo [4.3.0] non-5-ene is preferably used, but triethylamine is particularly preferable in view of economy, ease of handling, and ease of separation after the next step. The pKa of the conjugate acid of base B is the negative common logarithm of the acid dissociation constant Ka of BH ⁺ and is represented by the following [Equation 1].
[Formula 1]

(In the formula, [B], [H ⁺ ] and [BH ⁺ ] represent the molar concentrations of B, H ⁺ and BH ⁺ , respectively, and pKa uses a value in water at 25 ° C.)
The carboxylic acid anhydride or carboxylic acid halide and the base B represented by the chemical formula (5) are each 0.8 to 1.2 moles per 1 mole of the α-cyanoketone alkali metal salt represented by the chemical formula (4). It is preferable to use it.

  As the solvent used in the second step, ethers such as diethyl ether and THF can be used. It is preferable to use 1 to 10 mL of the solvent with respect to 1 g of the α-cyanoketone alkali metal salt represented by the chemical formula (4).

  The reaction temperature in the second step is preferably -20 ° C to 100 ° C. The reaction time is preferably 1 hour to 48 hours.

  The salt represented by the chemical formula (7) is obtained as a solid or liquid by concentrating the reaction mixture. Although it can be purified by recrystallization or column chromatography, it is usually used in the third step without purification.

  The third step is represented by the following reaction formula (5).

（式中、Ｒ_１、Ｒ_２は、水素原子、炭素数が１０以下のアルキル基、ハロゲン化アルキル基、アリール基、又は複素環基を示す。また、ＭＢ′はＢよりも共役酸のｐＫａが大きい塩基を示し、ＭはＬｉ、Ｎａ、又はＫを示す。）
ＭＢ′はＢよりも共役酸のｐＫａが大きい塩基であるが、これはＢよりも強い塩基と同義である。ＭＢ′はＢよりも共役酸のｐＫａが２以上大きいことが好ましい。ＭＢ′として具体的には、ＬｉＯＨ、ＮａＯＨ、ＫＯＨ、ＬｉＨ、ＮａＨ、ＫＨ、ＬｉＮＨ_２、ＮａＮＨ_２、ＫＮＨ_２、リチウムジイソプロピルアミドが好ましく用いられる。

(In the formula, R ₁ and R ₂ represent a hydrogen atom, an alkyl group having 10 or less carbon atoms, a halogenated alkyl group, an aryl group, or a heterocyclic group. MB ′ is a pKa of a conjugate acid rather than B. Represents a large base, and M represents Li, Na, or K.)
MB ′ is a base having a pKa of a conjugate acid larger than that of B, and this is synonymous with a base stronger than B. MB ′ preferably has a pKa of the conjugate acid of 2 or more larger than that of B. Specifically, as MB ′, LiOH, NaOH, KOH, LiH, NaH, KH, LiNH ₂ , NaNH ₂ , KNH ₂ , and lithium diisopropylamide are preferably used.

  The base MB ′ and the alkali metal M are preferably used in an amount of 0.8 to 1.2 mol with respect to 1 mol of the salt represented by the chemical formula (7).

  As the solvent used in the third step, ethers such as diethyl ether and THF, alcohols such as methanol and ethanol, and water can be used. It is preferable to use 1 to 10 mL of the solvent with respect to 1 g of the salt represented by the chemical formula (7).

  The reaction temperature in the third step is preferably -20 ° C to 100 ° C. The reaction time is preferably 1 hour to 48 hours.

The 2-cyano-1,3-diketonate salt represented by the chemical formula (1) can be isolated by recrystallization and / or column chromatography.
<Production Method 3: When producing 2-cyano-1,3-diketonate alkali metal salt>
When producing 2-cyano-1,3-diketonate alkali metal salt, the process is shortened to two steps regardless of the stability of 2-cyano-1,3-diketone represented by the chemical formula (6). Can be manufactured.
The first step is represented by the above reaction formula (1) as in Production Method 1. R ₁ is a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, trifluoromethyl group, pentafluoroethyl group, par Fluoro-n-propyl group, perfluoroisopropyl group, perfluoro-n-butyl group, perfluoroisobutyl group, perfluoro-sec-butyl group, perfluoro-tert-butyl group, phenyl group, 2-furanyl group, 2 It can carry out similarly to the 1st process of the manufacturing method 1 except a -thienyl group being preferable.
The second step is represented by the following reaction formula (6).

（式中、Ｒ_１、Ｒ_２は、水素原子、炭素数が１０以下のアルキル基、ハロゲン化アルキル基、アリール基、又は複素環基を示す。また、Ｍ及びＭ′はＬｉ、Ｎａ、又はＫを示し、ＸはＲ_２ＣＯＯ基、塩素原子、又は臭素原子を示す。）
Ｒ_１、Ｒ_２としては水素原子、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、トリフルオロメチル基、ペンタフルオロエチル基、パーフルオロ−ｎ−プロピル基、パーフルオロイソプロピル基、パーフルオロ−ｎ−ブチル基、パーフルオロイソブチル基、パーフルオロ−ｓｅｃ−ブチル基、パーフルオロ−ｔｅｒｔ−ブチル基、フェニル基、２−フラニル基、２−チエニル基が好ましく、Ｒ_１とＲ_２は同一でも異なっていてもよい。ＭとＭ′は同一でも異なっていてもよい。
前記化学式（４）で示されるα−シアノケトンアルカリ金属塩１モルに対し、前記化学式（５）で示されるカルボン酸無水物又はカルボン酸ハロゲン化物及びアルカリ金属水素化物ＭＨはそれぞれ０．８〜１．２モル用いることが好ましい。

(Wherein R ₁ and R ₂ represent a hydrogen atom, an alkyl group having 10 or less carbon atoms, a halogenated alkyl group, an aryl group, or a heterocyclic group. M and M ′ are Li, Na, or K represents X, and R represents an R ₂ COO group, a chlorine atom, or a bromine atom.)
R ₁ and R ₂ are hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, trifluoromethyl group, pentafluoroethyl. Group, perfluoro-n-propyl group, perfluoroisopropyl group, perfluoro-n-butyl group, perfluoroisobutyl group, perfluoro-sec-butyl group, perfluoro-tert-butyl group, phenyl group, 2-furanyl Group, 2-thienyl group is preferable, and R ₁ and R ₂ may be the same or different. M and M ′ may be the same or different.
The carboxylic acid anhydride or carboxylic acid halide and alkali metal hydride MH represented by the chemical formula (5) are each 0.8 to 1 mole per 1 mol of the α-cyanoketone alkali metal salt represented by the chemical formula (4). It is preferable to use 2 mol.

  As the solvent used in the second step, ethers such as diethyl ether and THF can be used. It is preferable to use 1 to 10 mL of the solvent with respect to 1 g of the α-cyanoketone alkali metal salt represented by the chemical formula (4).

  The reaction temperature in the second step is preferably -20 ° C to 100 ° C. The reaction time is preferably 1 hour to 48 hours.

  The 2-cyano-1,3-diketonate salt represented by the chemical formula (1) can be isolated by recrystallization and / or column chromatography.

With respect to the ionic liquid ionic liquids are a number of definitions have been proposed (ionic liquid II- tremendous progress and a variety of near future -, CMC Publishing, pp4-15,2006). In the present invention, the ionic liquid refers to a substance composed of only a cation and an anion, at least one of which is an organic ion, having a melting point of 100 ° C. or lower. Moreover, it is preferable that the ionic liquid of this invention is a liquid at least at normal temperature.

Anion Component An anion represented by the following chemical formula (8) is used for the anion component constituting the ionic liquid of the present invention. However, in formula, R < ₁ >, R < ₂ > shows a hydrogen atom, a C10 or less alkyl group, a halogenated alkyl group, an aryl group, or a heterocyclic group. A ring may be formed between R ₁ and R ₂ .

また、前記化学式（８）は下記化学式（１６）で示される共鳴混成体を代表して示したものであり、前記化学式（８）には下記化学式（１６）中のすべての共鳴構造が含まれる。

In addition, the chemical formula (8) represents a resonance hybrid represented by the following chemical formula (16), and the chemical formula (8) includes all the resonance structures in the following chemical formula (16). .

Ｒ_１、Ｒ_２としては水素原子、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、トリフルオロメチル基、ペンタフルオロエチル基、パーフルオロ−ｎ−プロピル基、パーフルオロイソプロピル基、パーフルオロ−ｎ−ブチル基、パーフルオロイソブチル基、パーフルオロ−ｓｅｃ−ブチル基、パーフルオロ−ｔｅｒｔ−ブチル基、フェニル基、２−フラニル基、２−チエニル基が好ましく、トリフルオロメチル基が特に好ましい。Ｒ_１とＲ_２は同一でも異なっていても良い。

R ₁ and R ₂ are hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, trifluoromethyl group, pentafluoroethyl. Group, perfluoro-n-propyl group, perfluoroisopropyl group, perfluoro-n-butyl group, perfluoroisobutyl group, perfluoro-sec-butyl group, perfluoro-tert-butyl group, phenyl group, 2-furanyl Group, 2-thienyl group is preferable, and trifluoromethyl group is particularly preferable. R ₁ and R ₂ may be the same or different.

  Preferable specific examples of the anion represented by the chemical formula (8) include a 3-cyano-1,1,1,5,5,5-hexafluoroacetylacetonate anion represented by the following chemical formula (9), and the following chemical formula (10). 3-cyano-1,1,1-trifluoroacetylacetonate anion represented by the following formula, 3-cyano-acetylacetonate anion represented by the following chemical formula (17), 4-cyano-2 represented by the following chemical formula (18) 2,6,6-tetramethyl-3,5-heptanedionate anion. Of these, 3-cyano-1,1,1,5,5,5-hexafluoroacetylacetonate anion is particularly preferable.

カチオン成分
本発明において用いられるカチオン成分は特に制限されない。ビス（トリフルオロメタンスルホニル）イミドアニオンやヘキサフルオロボレートアニオン等とイオン液体を形成するカチオンを本発明に於いても用いることができる。好ましいカチオンとしては下記化学式（１１）で示されるカチオンが挙げられる。但し、式中、Ｒ_１〜Ｒ_４は、水素原子、炭素数が２０以下のアルキル基、アルコキシアルキル基、トリアルキルシリルアルキル基、アルケニル基、アルキニル基、アリール基、又は複素環基を示し、Ｒ´_１〜Ｒ´_１０は水素原子、炭素数が１０以下のアルキル基、アルコキシアルキル基、トリアルキルシリルアルキル基、アルケニル基、アルキニル基、アリール基、又は複素環基を示す。

Cationic component The cationic component used in the present invention is not particularly limited. A cation that forms an ionic liquid with a bis (trifluoromethanesulfonyl) imide anion, a hexafluoroborate anion, or the like can also be used in the present invention. A preferable cation includes a cation represented by the following chemical formula (11). In the formula, R ₁ to R ₄ is a hydrogen atom, an alkyl group having 20 or less carbon atoms, an alkoxyalkyl group, a trialkylsilyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, R ′ _{1 to} R ′ ₁₀ represent a hydrogen atom, an alkyl group having 10 or less carbon atoms, an alkoxyalkyl group, a trialkylsilylalkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group.

Ｒ_１〜Ｒ_４としては水素原子、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ｎ−ペンチル基、ｎ−ヘキシル基、ｎ−ヘプチル基、ｎ−オクチル基、２−メトキシエチル基、トリメチルシリルメチル基、アリル基が好ましい。Ｒ´_１〜Ｒ´_１０としては水素原子、メチル基が好ましい。好ましいカチオンとしてより具体的には、下記化学式（１９）で示されるカチオンがあげられる。但し、式中、ｎは１〜１０の整数を示す。

R _{1 to} R ₄ include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, and an n-hexyl. Group, n-heptyl group, n-octyl group, 2-methoxyethyl group, trimethylsilylmethyl group and allyl group are preferred. R ′ _{1 to} R ′ ₁₀ are preferably a hydrogen atom or a methyl group. More specifically, preferred cations include cations represented by the following chemical formula (19). However, in formula, n shows the integer of 1-10.

イオン液体の合成方法
本発明のイオン液体は公知のイオン液体の合成法により合成することができる。例えば、下記反応式（７）〜（９）に示される合成法が挙げられる。式中、Ｃ^＋は本発明のイオン液体を構成するカチオン、Ｘ⁻はＣｌ⁻、Ｂｒ⁻、Ｉ⁻のいずれかのアニオン、Ｍ^＋はＬｉ^＋、Ｎａ^＋、Ｋ^＋、ＮＨ_４ ^＋、Ａｇ^＋のいずれかのカチオンを示す。

Synthesis Method of Ionic Liquid The ionic liquid of the present invention can be synthesized by a known ionic liquid synthesis method. For example, the synthesis method shown by following Reaction Formula (7)-(9) is mentioned. In the formula, C ⁺ is a cation constituting the ionic liquid of the present invention, X ⁻ is an anion of Cl ⁻ , Br ⁻ or I ⁻ , M ⁺ is Li ⁺ , Na ⁺ , K ⁺ , NH ₄ ⁺ , Ag ⁺ Indicates any cation.

上記反応式（７）に示したアニオン交換法によるイオン液体の合成方法について説明する。

A method for synthesizing an ionic liquid by the anion exchange method shown in the reaction formula (7) will be described.

<Anion raw material>
The anionic material, Li synthesized by the method of the present invention, Na, K, 2-cyano-1,3-diketonate salt _NH 4, Ag, or the like is used. The anion raw material is preferably used after being purified to a purity of 99% or more.

<Cation raw material>
The cation raw material can be a commercially available product or can be synthesized by a known method. As the cation raw material, a halide salt of the target cation is used. It is desirable that the cation raw material is used after being purified to a purity of 99% or more.

<Synthesis of ionic liquid>
The ionic liquid of the present invention can be synthesized by reacting so that the charge of the cation is equal to the charge of the anion. For example, a monovalent cation raw material and a monovalent anion raw material are reacted at a molar ratio of 1: 1, and a divalent cation raw material and a monovalent anion raw material are reacted at a molar ratio of 1: 2. As the reaction solvent, water, methanol, ethanol, acetonitrile, and acetone are preferable. The reaction is carried out by preparing solutions of the cation raw material and the anionic raw material and adding the other solution to one solution. The reaction can be carried out in air at room temperature. Although a halide salt is by-produced, when the filtration or ionic liquid is hydrophobic, the halide salt can be removed by washing with water.

Examples of the present invention will be specifically described below, but the present invention is not limited to them.
The purity of the synthesized compound is confirmed by elemental analysis or NMR. The NMR measuring apparatus uses JNM-ECA400 manufactured by JEOL Ltd., and the elemental analyzer uses CHN coder MT-6 manufactured by Yanaco Analytical Co., Ltd. In elemental analysis of compounds whose fluorine is equal to or more than hydrogen, tetrafluoromethane and tetrafluoroethylene are generated during decomposition of the sample, resulting in a negative error in the carbon analysis value, and these gases are separated from nitrogen by a nitrogen detector. Since it is detected at the same time, the nitrogen analysis value is biased positively. To prevent this, an excess of barium chloride dihydrate is added to the sample and analyzed. Barium chloride dihydrate is used for elemental analysis manufactured by Kishida Chemical.
[Example 1] Synthesis of sodium / 3-cyano-1,1,1,5,5,5-hexafluoroacetylacetonate (chemical formula (20))

＜３，３，３−トリフルオロ−１−シアノアセトン／ナトリウム塩の合成＞
全ての操作は窒素雰囲気で行う。また、使用する溶媒は脱水剤で十分に脱水し、窒素バブリングにより脱酸素したものを使用する。滴下ロートとジムロート冷却管を備えた５００ｍＬの３つ口フラスコに、ナトリウムエトキシド５１．０４ｇ（７５０．０ｍｍｏｌ）とアセトニトリル１０７．４５ｇ（２６１８ｍｍｏｌ）とを入れる。フラスコ内を攪拌しながら、トリフルオロ酢酸エチル１２４．４１ｇ（８７５．６ｍｍｏｌ）を室温で６０分間かけて滴下する。反応を完了させるために、滴下終了後６０分間攪拌を続け、さらに７０〜８０℃で６０分間還流する。溶媒を減圧留去し、残渣をアセトニトリル−シクロペンチルメチルエーテルより再結晶する。析出した結晶を濾過し、シクロペンチルメチルエーテルで洗浄、減圧乾燥する。その結果、淡黄色の固体として、３，３，３−トリフルオロ−１−シアノアセトン ナトリウム塩が９２．０７ｇ（収率７７％）得られる。
＜トリエチルアンモニウム／３−シアノ−１，１，１，５，５，５−ヘキサフルオロアセチルアセトネートの合成＞
全ての操作は窒素雰囲気で行う。また、使用する溶媒は脱水剤で十分に脱水し、窒素バブリングにより脱酸素したものを使用する。また、トリエチルアミンは予め蒸留精製したものを使用する。滴下ロートを備えた１Ｌの３つ口フラスコに、３，３，３−トリフルオロ−１−シアノアセトン／ナトリウム塩６４．６２ｇ（４０６．３ｍｍｏｌ）とジエチルエーテル３００ｍＬとトリエチルアミン４１．１１ｇ（４０６．３ｍｍｏｌ）とを入れる。フラスコ内を攪拌し、５〜１０℃に冷却しながら、トリフルオロ酢酸無水物８５．３４ｇ（４０６．３ｍｍｏｌ）を１２０分間かけて滴下する。反応を完了させるために、添加終了後、室温で２４時間攪拌を続ける。反応液にジクロロメタン１．９Ｌを加えると沈殿が析出する。沈殿を濾過して除去し、濾液から溶媒を減圧留去すると赤色の液体として、トリエチルアンモニウム ３−シアノ−１，１，１，５，５，５−ヘキサフルオロアセチルアセトネートが１０４．１０ｇ（収率７７％）得られる。
＜ナトリウム／３−シアノ−１，１，１，５，５，５−ヘキサフルオロアセチルアセトネートの合成＞
全ての操作は窒素雰囲気で行う。また、使用する溶媒は脱水剤で十分に脱水し、窒素バブリングにより脱酸素したものを使用する。滴下ロートを備えた１Ｌの３つ口フラスコに、水素化ナトリウム（純度６０％、４０％オイル含有）１３．６８ｇ（３４２．０ｍｍｏｌ）とテトラヒドロフラン２２８ｍＬとを入れる。フラスコ内を攪拌し、１０〜１５℃に冷却しながら、トリエチルアンモニウム／３−シアノ−１，１，１，５，５，５−ヘキサフルオロアセチルアセトネート１０３．９４ｇ（３１１．０ｍｍｏｌ）をテトラヒドロフラン２２８ｍＬに溶かした溶液を９０分間かけて滴下する。反応を完了させるために、添加終了後、室温で９０分間攪拌を続ける。溶媒を減圧留去し、残渣をジクロロメタンで洗浄、濾過、減圧乾燥する。得られた固体をカラムクロマトグラフィーで精製し、さらに酢酸エチル−ジクロロメタンより再結晶する。析出した結晶を濾過し、ジクロロメタンで洗浄、減圧乾燥する。その結果、白色固体としてナトリウム ３−シアノ−１，１，１，５，５，５−ヘキサフルオロアセチルアセトネートが２７．０７ｇ（収率３４％）得られる。合成した化合物１．９２２ｍｇに塩化バリウム２水和物８．０８３ｍｇを添加したものを元素分析する。結果を下記に示す。
〔元素分析値〕
理論値：Ｃ５．４３／Ｈ１．３３／Ｎ１．０５
分析値：Ｃ５．５４／Ｈ１．３１／Ｎ０．９３
〔実施例２〕ナトリウム／３−シアノ−１，１，１−トリフルオロアセチルアセトネート（化学式（２１））の合成

<Synthesis of 3,3,3-trifluoro-1-cyanoacetone / sodium salt>
All operations are performed in a nitrogen atmosphere. The solvent to be used is one that has been sufficiently dehydrated with a dehydrating agent and deoxygenated by nitrogen bubbling. Sodium ethoxide 51.04 g (750.0 mmol) and acetonitrile 107.45 g (2618 mmol) are placed in a 500 mL three-necked flask equipped with a dropping funnel and a Dimroth condenser. While stirring the inside of the flask, 124.41 g (875.6 mmol) of ethyl trifluoroacetate is added dropwise at room temperature over 60 minutes. In order to complete the reaction, stirring is continued for 60 minutes after completion of the dropwise addition, and the mixture is further refluxed at 70 to 80 ° C. for 60 minutes. The solvent is distilled off under reduced pressure, and the residue is recrystallized from acetonitrile-cyclopentyl methyl ether. The precipitated crystals are filtered, washed with cyclopentyl methyl ether, and dried under reduced pressure. As a result, 92.07 g (yield 77%) of 3,3,3-trifluoro-1-cyanoacetone sodium salt is obtained as a pale yellow solid.
<Synthesis of triethylammonium / 3-cyano-1,1,1,5,5,5-hexafluoroacetylacetonate>
All operations are performed in a nitrogen atmosphere. The solvent to be used is one that has been sufficiently dehydrated with a dehydrating agent and deoxygenated by nitrogen bubbling. In addition, triethylamine is distilled and purified in advance. In a 1 L three-necked flask equipped with a dropping funnel, 64.62 g (406.3 mmol) of 3,3,3-trifluoro-1-cyanoacetone / sodium salt, 300 mL of diethyl ether and 41.11 g (406.3 mmol) of triethylamine were added. ) While the flask is stirred and cooled to 5 to 10 ° C., 85.34 g (406.3 mmol) of trifluoroacetic anhydride is added dropwise over 120 minutes. To complete the reaction, stirring is continued for 24 hours at room temperature after the end of the addition. When 1.9 L of dichloromethane is added to the reaction solution, a precipitate is deposited. The precipitate was removed by filtration, and the solvent was distilled off from the filtrate under reduced pressure. As a red liquid, 104.10 g (yield) of triethylammonium 3-cyano-1,1,1,5,5,5-hexafluoroacetylacetonate was obtained. Rate 77%).
<Synthesis of sodium / 3-cyano-1,1,1,5,5,5-hexafluoroacetylacetonate>
All operations are performed in a nitrogen atmosphere. The solvent to be used is one that has been sufficiently dehydrated with a dehydrating agent and deoxygenated by nitrogen bubbling. 13.68 g (342.0 mmol) of sodium hydride (purity 60%, containing 40% oil) and 228 mL of tetrahydrofuran are placed in a 1 L three-necked flask equipped with a dropping funnel. While stirring the flask and cooling to 10 to 15 ° C., 103.94 g (311.0 mmol) of triethylammonium / 3-cyano-1,1,1,5,5,5-hexafluoroacetylacetonate was added to 228 mL of tetrahydrofuran. The solution dissolved in is dropped over 90 minutes. To complete the reaction, continue stirring at room temperature for 90 minutes after the addition is complete. The solvent is distilled off under reduced pressure, and the residue is washed with dichloromethane, filtered and dried under reduced pressure. The obtained solid is purified by column chromatography and recrystallized from ethyl acetate-dichloromethane. The precipitated crystals are filtered, washed with dichloromethane and dried under reduced pressure. As a result, 27.07 g (34% yield) of sodium 3-cyano-1,1,1,5,5,5-hexafluoroacetylacetonate is obtained as a white solid. Elemental analysis is performed on the compound obtained by adding 8.083 mg of barium chloride dihydrate to 1.922 mg of the synthesized compound. The results are shown below.
[Elemental analysis values]
Theoretical value: C5.43 / H1.33 / N1.05
Analytical value: C5.54 / H1.31 / N0.93
[Example 2] Synthesis of sodium / 3-cyano-1,1,1-trifluoroacetylacetonate (chemical formula (21))

＜シアノアセトン／ナトリウム塩の合成＞
全ての操作は窒素雰囲気で行う。また、使用する溶媒は脱水剤で十分に脱水し、窒素バブリングにより脱酸素したものを使用する。ジムロート冷却管を備えた１Ｌの３つ口フラスコに、ナトリウムメトキシド８１．０５ｇ（１．５００ｍｏｌ）とアセトニトリル４０２．３０ｇ（９．８００ｍｏｌ）と酢酸エチル１５８．５８ｇ（１．８００ｍｏｌ）とを入れる。フラスコ内を攪拌しながら、７５℃で２７０分間還流する。室温まで冷却した後、ロータリーエバポレーターで濃縮する。析出した結晶を濾過し、アセトニトリルで洗浄、減圧乾燥する。その結果、白色固体として、シアノアセトン ナトリウム塩が９９．６１ｇ（収率６３％）得られる。
＜ナトリウム／３−シアノ−１，１，１−トリフルオロアセチルアセトネートの合成＞
全ての操作は窒素雰囲気で行う。また、使用する溶媒は脱水剤で十分に脱水し、窒素バブリングにより脱酸素したものを使用する。滴下ロートを備えた１００ｍＬの３つ口フラスコに、水素化ナトリウム１．２５ｇ（５２．１ｍｍｏｌ）とシアノアセトン／ナトリウム塩５．００ｇ（４７．６ｍｍｏｌ）とジエチルエーテル５０ｍＬとを入れる。フラスコ内を攪拌し、０℃に冷却しながら、トリフルオロ酢酸無水物１０．４９ｇ（５０．０ｍｍｏｌ）をジエチルエーテル２０ｍＬに溶かした溶液を６０分間かけて滴下する。反応を完了させるために、添加終了後、０℃で１８時間攪拌を続ける。反応混合物を濾過し、濾渣をテトラヒドロフラン１５０ｍＬに懸濁する。不溶物を濾別し、濾液を乾固する。得られた固体をカラムクロマトグラフィーで精製し、さらに酢酸エチル−ジクロロメタンより再結晶する。析出した結晶を濾過し、ジクロロメタンで洗浄、減圧乾燥する。その結果、白色固体として、ナトリウム ３−シアノ−１，１，１−トリフルオロアセチルアセトネートが１．３９ｇ（収率１５％）得られる。合成した化合物２．１２７ｍｇに塩化バリウム２水和物８．０８０ｍｇを添加したものを元素分析する。結果を下記に示す。
〔元素分析値〕
理論値：Ｃ７．４７／Ｈ１．６１／Ｎ１．４５
分析値：Ｃ７．８０／Ｈ１．６７／Ｎ１．３３
〔実施例３〕１−ブチル−３−メチルイミダゾリウム／３−シアノ−１，１，１，５，５，５−ヘキサフルオロアセチルアセトネート（化学式（１２））の合成

<Synthesis of cyanoacetone / sodium salt>
All operations are performed in a nitrogen atmosphere. The solvent to be used is one that has been sufficiently dehydrated with a dehydrating agent and deoxygenated by nitrogen bubbling. Sodium methoxide 81.05 g (1.500 mol), acetonitrile 402.30 g (9.800 mol), and ethyl acetate 158.58 g (1.800 mol) are placed in a 1 L three-necked flask equipped with a Dimroth condenser. While stirring in the flask, the mixture is refluxed at 75 ° C. for 270 minutes. After cooling to room temperature, the mixture is concentrated on a rotary evaporator. The precipitated crystals are filtered, washed with acetonitrile, and dried under reduced pressure. As a result, 99.61 g (yield 63%) of cyanoacetone sodium salt is obtained as a white solid.
<Synthesis of sodium / 3-cyano-1,1,1-trifluoroacetylacetonate>
All operations are performed in a nitrogen atmosphere. The solvent to be used is one that has been sufficiently dehydrated with a dehydrating agent and deoxygenated by nitrogen bubbling. A 100 mL three-necked flask equipped with a dropping funnel is charged with 1.25 g (52.1 mmol) of sodium hydride, 5.00 g (47.6 mmol) of cyanoacetone / sodium salt, and 50 mL of diethyl ether. While stirring the inside of the flask and cooling to 0 ° C., a solution of 10.49 g (50.0 mmol) of trifluoroacetic anhydride in 20 mL of diethyl ether is added dropwise over 60 minutes. To complete the reaction, stirring is continued at 0 ° C. for 18 hours after the end of the addition. The reaction mixture is filtered and the residue is suspended in 150 mL of tetrahydrofuran. Insoluble materials are filtered off, and the filtrate is dried. The obtained solid is purified by column chromatography and recrystallized from ethyl acetate-dichloromethane. The precipitated crystals are filtered, washed with dichloromethane and dried under reduced pressure. As a result, 1.39 g (yield 15%) of sodium 3-cyano-1,1,1-trifluoroacetylacetonate is obtained as a white solid. Elemental analysis is performed on 2.127 mg of the synthesized compound with addition of 8.080 mg of barium chloride dihydrate. The results are shown below.
[Elemental analysis values]
Theoretical value: C7.47 / H1.61 / N1.45
Analytical value: C7.80 / H1.67 / N1.33
[Example 3] Synthesis of 1-butyl-3-methylimidazolium / 3-cyano-1,1,1,5,5,5-hexafluoroacetylacetonate (chemical formula (12))

＜１−ブチル−３−メチルイミダゾリウム／クロライドの合成＞
全ての操作は窒素雰囲気で行う。また、使用する溶媒は脱水剤で十分に脱水し、窒素バブリングにより脱酸素したものを使用する。また、１−メチルイミダゾールは予め蒸留精製したものを使用する。ジムロート冷却管を備えた５００ｍＬの３つ口フラスコに、１−メチルイミダゾール７０．１０ｇ（８５３．８ｍｍｏｌ）と１−クロロブタン１５８．００ｇ（１７０７ｍｍｏｌ）とを入れる。９０℃で３０時間攪拌し、室温まで冷却する。生成した固体をジエチルエーテルで洗浄し、濾過、減圧乾燥する。その結果、白色固体として、１−ブチル−３−メチルイミダゾリウム クロライドが１４６．７５ｇ（収率９８％）得られる。元素分析の結果を下記に示す。
〔元素分析値〕
理論値：Ｃ５５．０１／Ｈ８．６６／Ｎ１６．０４
分析値：Ｃ５５．５０／Ｈ８．３９／Ｎ１６．７２
＜１−ブチル−３−メチルイミダゾリウム／３−シアノ−１，１，１，５，５，５−ヘキサフルオロアセチルアセトネートの合成＞
実施例１で合成したナトリウム／３−シアノ−１，１，１，５，５，５−ヘキサフルオロアセチルアセトネート０．５３５５ｇ（２．１００ｍｍｏｌ）と１−ブチル−３−メチルイミダゾリウム／クロライド０．３６６７ｇ（２．０９９ｍｍｏｌ）とを窒素雰囲気下で別々の５０ｍＬナス型フラスコに秤量する。それぞれのフラスコにアセトニトリル１ｍＬを加え溶液とする。室温で攪拌しながら１−ブチル−３−メチルイミダゾリウム／クロライドの溶液にナトリウム／３−シアノ−１，１，１，５，５，５−ヘキサフルオロアセチルアセトネートの溶液を添加する。フラスコに残った溶液はアセトニトリル０．５ｍＬで洗い流し、１−ブチル−３−メチルイミダゾリウム／クロライドの溶液に残さず加える。添加と同時に白色の沈殿が生成する。反応を完了させるために、添加終了後、さらに２０時間攪拌を続ける。アセトニトリルを減圧留去し、水１０ｍＬとジクロロメタン１０ｍＬを加えると透明な２層の溶液となる。有機層（下層）を分離し、水１０ｍｌで２回洗浄する。ジクロロメタンを減圧留去した後、６６Ｐａ、６０℃で１時間乾燥する。その結果、黄色液体として、１−ブチル−３−メチルイミダゾリウム ３−シアノ−１，１，１，５，５，５−ヘキサフルオロアセチルアセトネートが０．６５ｇ（収率８３％）得られる。合成したイオン液体の構造はＮＭＲにて確認した。結果を下記に示す。

<Synthesis of 1-butyl-3-methylimidazolium / chloride>
All operations are performed in a nitrogen atmosphere. The solvent to be used is one that has been sufficiently dehydrated with a dehydrating agent and deoxygenated by nitrogen bubbling. Also, 1-methylimidazole is distilled and purified in advance. In a 500 mL three-necked flask equipped with a Dimroth condenser, 70.10 g (853.8 mmol) of 1-methylimidazole and 158.00 g (1707 mmol) of 1-chlorobutane are placed. Stir at 90 ° C. for 30 hours and cool to room temperature. The resulting solid is washed with diethyl ether, filtered and dried under reduced pressure. As a result, 146.75 g (yield 98%) of 1-butyl-3-methylimidazolium chloride is obtained as a white solid. The results of elemental analysis are shown below.
[Elemental analysis values]
Theoretical value: C55.01 / H8.66 / N16.04
Analytical value: C55.50 / H8.39 / N16.72
<Synthesis of 1-butyl-3-methylimidazolium / 3-cyano-1,1,1,5,5,5-hexafluoroacetylacetonate>
Sodium / 3-cyano-1,1,1,5,5,5-hexafluoroacetylacetonate 0.5355 g (2.100 mmol) synthesized in Example 1 and 1-butyl-3-methylimidazolium / chloride 0 3667 g (2.099 mmol) is weighed into a separate 50 mL eggplant flask under a nitrogen atmosphere. Add 1 mL of acetonitrile to each flask to make a solution. Add the sodium / 3-cyano-1,1,1,5,5,5-hexafluoroacetylacetonate solution to the 1-butyl-3-methylimidazolium / chloride solution with stirring at room temperature. Rinse the remaining solution in the flask with 0.5 mL of acetonitrile and add to the 1-butyl-3-methylimidazolium / chloride solution. A white precipitate forms upon addition. To complete the reaction, stirring is continued for an additional 20 hours after the addition is complete. Acetonitrile is distilled off under reduced pressure, and 10 mL of water and 10 mL of dichloromethane are added to form a transparent two-layer solution. The organic layer (lower layer) is separated and washed twice with 10 ml of water. Dichloromethane is distilled off under reduced pressure, followed by drying at 66 Pa and 60 ° C. for 1 hour. As a result, 0.65 g (yield 83%) of 1-butyl-3-methylimidazolium 3-cyano-1,1,1,5,5,5-hexafluoroacetylacetonate is obtained as a yellow liquid. The structure of the synthesized ionic liquid was confirmed by NMR. The results are shown below.

[NMR spectral data]
¹ H-NMR (400 MHz, CD ₂ Cl ₂ )
δ (ppm) 9.38 (1H, s), 7.36 (1H, d, J = 1.8 Hz), 7.34 (1H, s), 4.22 (2H, t, J = 7.3 Hz) ), 3.98 (3H, s), 1.85 (2H, quint, J = 7.6 Hz), 1.36 (2H, sext, J = 7.6 Hz), 0.95 (3H, t, J = 7.3Hz)
¹³ C-NMR (100 MHz, CD ₂ Cl ₂ )
δ (ppm) 175.00 (q, J _CF = 33 Hz), 137.51, 123.97, 122.67, 119.52, 117.87 (q, J _CF = 292 Hz), 76.58, 50. 33, 36.71, 32.49, 19.76, 13.42
Example 4 Synthesis of 1-methyl-1-pentylpyrrolidinium / 3-cyano-1,1,1,5,5,5-hexafluoroacetylacetonate (chemical formula (13))

＜１−メチル−１−ペンチルピロリジニウム／ブロマイドの合成＞
全ての操作は窒素雰囲気で行う。また、使用する溶媒は脱水剤で十分に脱水し、窒素バブリングにより脱酸素したものを使用する。また、１−メチルピロリジンは予め蒸留精製したものを使用する。滴下ロートとジムロート冷却管を備えた５００ｍＬの３つ口フラスコに、１−メチルピロリジン２２．９３ｇ（２６９．３ｍｍｏｌ）とシクロペンチルメチルエーテル１５０ｍＬとを入れる。９０℃で攪拌しながら１−ブロモペンタン８１．６１ｇ（５４０．３ｍｍｏｌ）を４時間かけて滴下する。そのまま９０℃で１４時間攪拌した後室温へ冷却する。生成した沈殿をシクロペンチルメチルエーテルで洗浄し、濾過、減圧乾燥する。その結果、白色固体として、１−メチル−１−ペンチルピロリジニウム ブロマイドが６１．８７ｇ（収率９７％）得られる。元素分析の結果を下記に示す。
〔元素分析値〕
理論値：Ｃ５０．８５／Ｈ９．３９／Ｎ５．９３
分析値：Ｃ５１．６８／Ｈ１０．１６／Ｎ５．７２
＜１−メチル−１−ペンチルピロリジニウム／３−シアノ−１，１，１，５，５，５−ヘキサフルオロアセチルアセトネートの合成＞
実施例１で合成したナトリウム／３−シアノ−１，１，１，５，５，５−ヘキサフルオロアセチルアセトネート１．０８５ｇ（４．２５４ｍｍｏｌ）と１−メチル−１−ペンチルピロリジニウム／ブロマイド１．００５ｇ（４．２５５ｍｍｏｌ）とを窒素雰囲気下で別々の５０ｍＬナス型フラスコに秤量する。それぞれのフラスコにアセトニトリル２ｍＬを加え溶液とする。室温で攪拌しながら１−メチル−１−ペンチルピロリジニウム・ブロマイドの溶液にナトリウム／３−シアノ−１，１，１，５，５，５−ヘキサフルオロアセチルアセトネートの溶液を添加する。フラスコに残った溶液はアセトニトリル１ｍＬで洗い流し、１−メチル−１−ペンチルピロリジニウム／ブロマイドの溶液に残さず加える。添加と同時に白色の沈殿が生成する。反応を完了させるために、添加終了後、さらに２０時間攪拌を続ける。アセトニトリルを減圧留去し、水１０ｍＬとジクロロメタン１０ｍＬを加えると透明な２層の溶液となる。有機層（下層）を分離し、水１０ｍＬで２回洗浄する。ジクロロメタンを減圧留去した後、６６Ｐａ、６０℃で１時間乾燥する。その結果、淡黄色液体として、１−メチル−１−ペンチルピロリジニウム ３−シアノ−１，１，１，５，５，５−ヘキサフルオロアセチルアセトネートが１．４１ｇ（収率８５％）得られる。合成したイオン液体の構造はＮＭＲにて確認した。結果を下記に示す。

<Synthesis of 1-methyl-1-pentylpyrrolidinium / bromide>
All operations are performed in a nitrogen atmosphere. The solvent to be used is one that has been sufficiently dehydrated with a dehydrating agent and deoxygenated by nitrogen bubbling. Also, 1-methylpyrrolidine is distilled and purified in advance. In a 500 mL three-necked flask equipped with a dropping funnel and a Dimroth condenser, 22.93 g (269.3 mmol) of 1-methylpyrrolidine and 150 mL of cyclopentyl methyl ether are placed. While stirring at 90 ° C., 81.61 g (540.3 mmol) of 1-bromopentane is added dropwise over 4 hours. The mixture is stirred at 90 ° C. for 14 hours and then cooled to room temperature. The formed precipitate is washed with cyclopentyl methyl ether, filtered and dried under reduced pressure. As a result, 61.87 g (yield 97%) of 1-methyl-1-pentylpyrrolidinium bromide is obtained as a white solid. The results of elemental analysis are shown below.
[Elemental analysis values]
Theoretical value: C50.85 / H9.39 / N5.93
Analytical value: C51.68 / H10.16 / N5.72
<Synthesis of 1-methyl-1-pentylpyrrolidinium / 3-cyano-1,1,1,5,5,5-hexafluoroacetylacetonate>
1.085 g (4.254 mmol) of sodium / 3-cyano-1,1,1,5,5,5-hexafluoroacetylacetonate synthesized in Example 1 and 1-methyl-1-pentylpyrrolidinium / bromide 1.005 g (4.255 mmol) is weighed into a separate 50 mL eggplant flask under a nitrogen atmosphere. Add 2 mL of acetonitrile to each flask to make a solution. While stirring at room temperature, a solution of sodium / 3-cyano-1,1,1,5,5,5-hexafluoroacetylacetonate is added to a solution of 1-methyl-1-pentylpyrrolidinium bromide. The solution remaining in the flask is rinsed with 1 mL of acetonitrile and added to the 1-methyl-1-pentylpyrrolidinium / bromide solution. A white precipitate forms upon addition. To complete the reaction, stirring is continued for an additional 20 hours after the addition is complete. Acetonitrile is distilled off under reduced pressure, and 10 mL of water and 10 mL of dichloromethane are added to form a transparent two-layer solution. Separate the organic layer (lower layer) and wash twice with 10 mL of water. Dichloromethane is distilled off under reduced pressure, followed by drying at 66 Pa and 60 ° C. for 1 hour. As a result, 1.41 g (yield 85%) of 1-methyl-1-pentylpyrrolidinium 3-cyano-1,1,1,5,5,5-hexafluoroacetylacetonate was obtained as a pale yellow liquid. It is done. The structure of the synthesized ionic liquid was confirmed by NMR. The results are shown below.

[NMR spectral data]
¹ H-NMR (400 MHz, CDCl ₃ )
δ (ppm) 3.59 (4H, m), 3.37 (2H, m), 3.11 (3H, s), 2.28 (4H, m), 1.78 (2H, m), 1 .36 (4H, m), 0.91 (3H, t, J = 6.9 Hz)
¹³ C-NMR (100 MHz, CDCl ₃ )
δ (ppm) 174.64 (q, J _CF = 33 Hz), 119.66, 117.43 (q, J _CF = 292 Hz), 76.72, 64.81, 64.56, 48.43, 28. 22, 23.53, 22.05, 21.61, 13.62
[Example 5] Synthesis of 1-butyl-3-methylimidazolium / 3-cyano-1,1,1-trifluoroacetylacetonate (chemical formula (14))

＜１−ブチル−３−メチルイミダゾリウム／３−シアノ−１，１，１−トリフルオロアセチルアセトネートの合成＞
実施例２で合成したナトリウム／３−シアノ−１，１，１−トリフルオロアセチルアセトネート０．６１１１ｇ（３．０３９ｍｍｏｌ）と実施例３で合成した１−ブチル−３−メチルイミダゾリウム／クロライド０．５３０４ｇ（３．０３７ｍｍｏｌ）とを窒素雰囲気下で別々の５０ｍＬナス型フラスコに秤量する。それぞれのフラスコにメタノール１ｍＬを加え溶液とする。室温で攪拌しながら１−ブチル−３−メチルイミダゾリウム／クロライドの溶液にナトリウム／３−シアノ−１，１，１−トリフルオロアセチルアセトネートの溶液を添加する。フラスコに残った溶液はメタノール０．５ｍＬで洗い流し、１−ブチル−３−メチルイミダゾリウム／クロライドの溶液に残さず加える。添加と同時に白色の沈殿が生成する。反応を完了させるために、添加終了後、さらに１６時間攪拌を続ける。メタノールを減圧留去し、ジクロロメタン１０ｍＬを加え不溶物を濾別する。ジクロロメタンを減圧留去し、再びジクロロメタン１０ｍＬを加え不溶物を濾別する。ジクロロメタンを減圧留去した後、６６Ｐａ、６０℃で１時間乾燥する。その結果、淡黄色液体として、１−ブチル−３−メチルイミダゾリウム ３−シアノ−１，１，１−トリフルオロアセチルアセトネートが０．６８ｇ（収率７１％）得られる。合成したイオン液体の構造はＮＭＲにて確認した。結果を下記に示す。

<Synthesis of 1-butyl-3-methylimidazolium / 3-cyano-1,1,1-trifluoroacetylacetonate>
0.6111 g (3.039 mmol) of sodium / 3-cyano-1,1,1-trifluoroacetylacetonate synthesized in Example 2 and 1-butyl-3-methylimidazolium / chloride synthesized in Example 3 5304 g (3.037 mmol) are weighed into separate 50 mL eggplant flasks under a nitrogen atmosphere. Add 1 mL of methanol to each flask to make a solution. Add the solution of sodium / 3-cyano-1,1,1-trifluoroacetylacetonate to the 1-butyl-3-methylimidazolium / chloride solution with stirring at room temperature. Rinse the solution remaining in the flask with 0.5 mL of methanol and add to the 1-butyl-3-methylimidazolium / chloride solution. A white precipitate forms upon addition. To complete the reaction, stirring is continued for an additional 16 hours after the addition is complete. Methanol is distilled off under reduced pressure, 10 mL of dichloromethane is added, and insoluble matters are filtered off. Dichloromethane is distilled off under reduced pressure, 10 mL of dichloromethane is added again, and insoluble matters are filtered off. Dichloromethane is distilled off under reduced pressure, followed by drying at 66 Pa and 60 ° C. for 1 hour. As a result, 0.68 g (yield 71%) of 1-butyl-3-methylimidazolium 3-cyano-1,1,1-trifluoroacetylacetonate is obtained as a pale yellow liquid. The structure of the synthesized ionic liquid was confirmed by NMR. The results are shown below.

[NMR spectral data]
¹ H-NMR (400 MHz, CDCl ₃ )
δ (ppm) 9.82 (1H, s), 7.51 (1H, d, J = 1.4 Hz), 7.45 (1H, s), 4.26 (2H, t, J = 7.6 Hz) ), 4.03 (3H, s), 2.27 (3H, s), 1.87 (2H, quint, J = 7.6 Hz), 1.36 (2H, sext, J = 7.4 Hz), 0.95 (3H, t, J = 7.3Hz)
¹³ C-NMR (100 MHz, CDCl ₃ )
δ (ppm) 195.79, 173.26 (q, J _CF = 31 Hz), 137.30, 123.71, 122.19, 121.95, 118.30 (q, J _CF = 291 Hz), 82. 71, 49.78, 36.35, 32.06, 29.40, 19.37, 13.30
[Example 6] Synthesis of 1-hexyl-1-methylpiperidinium / 3-cyano-1,1,1-trifluoroacetylacetonate (chemical formula (15))

＜１−ヘキシル−１−メチルピペリジニウム／ブロマイドの合成＞
全ての操作は窒素雰囲気で行う。また、使用する溶媒は脱水剤で十分に脱水し、窒素バブリングにより脱酸素したものを使用する。また、１−メチルピペリジンは予め蒸留精製したものを使用する。滴下ロートとジムロート冷却管を備えた５００ｍＬの３つ口フラスコに、１−メチルピペリジン１９．５８ｇ（１９７．５ｍｍｏｌ）とシクロペンチルメチルエーテル１００ｍＬとを入れる。１１０℃で攪拌しながら１−ブロモヘキサン６５．８６ｇ（３９９．０ｍｍｏｌ）を４時間かけて滴下する。そのまま１１０℃で１６時間攪拌した後室温へ冷却する。生成した沈殿をシクロペンチルメチルエーテルで洗浄し、濾過、減圧乾燥する。その結果、白色固体として、１−ヘキシル−１−メチルピペリジニウム ブロマイドが５１．１２ｇ（収率９８％）得られる。元素分析の結果を下に示す。
〔元素分析値〕
理論値：Ｃ５４．５４／Ｈ９．９２／Ｎ５．３０
分析値：Ｃ５４．９０／Ｈ１０．４２／Ｎ６．０７
＜１−ヘキシル−１−メチルピペリジニウム／３−シアノ−１，１，１−トリフルオロアセチルアセトネートの合成＞
実施例２で合成したナトリウム／３−シアノ−１，１，１−トリフルオロアセチルアセトネート０．６０２１ｇ（２．９９４ｍｍｏｌ）と１−ヘキシル−１−メチルピペリジニウム／ブロマイド０．７９１０ｇ（２．９９３ｍｍｏｌ）とを窒素雰囲気下で別々の５０ｍＬナス型フラスコに秤量する。それぞれのフラスコにメタノール１ｍＬを加え溶液とする。室温で攪拌しながら１−ヘキシル−１−メチルピペリジニウム／ブロマイドの溶液にナトリウム・３−シアノ−１，１，１−トリフルオロアセチルアセトネートの溶液を添加する。フラスコに残った溶液はメタノール０．５ｍＬで洗い流し、１−ヘキシル−１−メチルピペリジニウム／ブロマイドの溶液に残さず加える。添加と同時に白色の沈殿が生成する。反応を完了させるために、添加終了後、さらに１６時間攪拌を続ける。メタノールを減圧留去し、水１０ｍＬとジクロロメタン１０ｍＬを加えると透明な２層の溶液となる。有機層（下層）を分離し、水１０ｍＬで２回洗浄する。ジクロロメタンを減圧留去した後、６６Ｐａ、６０℃で１時間乾燥する。その結果、淡黄色液体として、１−ヘキシル−１−メチルピペリジニウム ３−シアノ−１，１，１−トリフルオロアセチルアセトネートが０．９８ｇ（収率９３％）得られる。合成したイオン液体の構造はＮＭＲにて確認した。結果を下記に示す。

<Synthesis of 1-hexyl-1-methylpiperidinium / bromide>
All operations are performed in a nitrogen atmosphere. The solvent to be used is one that has been sufficiently dehydrated with a dehydrating agent and deoxygenated by nitrogen bubbling. Further, 1-methylpiperidine is used after being purified by distillation. In a 500 mL three-necked flask equipped with a dropping funnel and a Dimroth condenser, 19.58 g (197.5 mmol) of 1-methylpiperidine and 100 mL of cyclopentyl methyl ether are placed. While stirring at 110 ° C., 65.86 g (399.0 mmol) of 1-bromohexane is added dropwise over 4 hours. The mixture is stirred at 110 ° C. for 16 hours and then cooled to room temperature. The formed precipitate is washed with cyclopentyl methyl ether, filtered and dried under reduced pressure. As a result, 51.12 g (yield 98%) of 1-hexyl-1-methylpiperidinium bromide is obtained as a white solid. The results of elemental analysis are shown below.
[Elemental analysis values]
Theoretical value: C54.54 / H9.92 / N5.30
Analytical value: C54.90 / H10.42 / N6.07
<Synthesis of 1-hexyl-1-methylpiperidinium / 3-cyano-1,1,1-trifluoroacetylacetonate>
0.6021 g (2.994 mmol) of sodium / 3-cyano-1,1,1-trifluoroacetylacetonate synthesized in Example 2 and 0.7910 g of 1-hexyl-1-methylpiperidinium / bromide (2. 993 mmol) in a separate 50 mL eggplant-shaped flask under a nitrogen atmosphere. Add 1 mL of methanol to each flask to make a solution. While stirring at room temperature, a solution of sodium 3-cyano-1,1,1-trifluoroacetylacetonate is added to a solution of 1-hexyl-1-methylpiperidinium / bromide. Rinse the solution remaining in the flask with 0.5 mL of methanol and add to the 1-hexyl-1-methylpiperidinium / bromide solution. A white precipitate forms upon addition. To complete the reaction, stirring is continued for an additional 16 hours after the addition is complete. Methanol is distilled off under reduced pressure, and 10 mL of water and 10 mL of dichloromethane are added to form a transparent two-layer solution. Separate the organic layer (lower layer) and wash twice with 10 mL of water. Dichloromethane is distilled off under reduced pressure, followed by drying at 66 Pa and 60 ° C. for 1 hour. As a result, 0.98 g (yield 93%) of 1-hexyl-1-methylpiperidinium 3-cyano-1,1,1-trifluoroacetylacetonate is obtained as a pale yellow liquid. The structure of the synthesized ionic liquid was confirmed by NMR. The results are shown below.

[NMR spectral data]
¹ H-NMR (400 MHz, CDCl ₃ )
δ (ppm) 3.45 (4H, m), 3.38 (2H, m), 3.14 (3H, s), 2.36 (3H, s), 1.91 (4H, m), 1 .74 (4H, m), 1.33 (6H, m), 0.88 (3H, t, J = 7.1 Hz)
¹³ C-NMR (100 MHz, CDCl ₃ )
δ (ppm) 195.90, 173.25 (q, J _CF = 30 Hz), 122.42, 118.82 (q, J _CF = 293 Hz), 82.79, 64.15, 61.25, 47. 81, 31.12, 30.41, 25.92, 22.33, 21.79, 20.79, 20.03, 13.83

The present invention relates to a method for producing a 2-cyano-1,3-diketonate salt. It is possible to produce a 2-cyano-1,3-diketonate salt having a CF ₃ group by using acetonitrile with relatively low toxicity as a reagent for introducing a cyano group. Furthermore, a novel ionic liquid can be provided using 2-cyano-1,3-diketonate salt as a raw material.

Claims (12)

The following chemical formula (1)

(In the formula, R ₁ and R ₂ represent a hydrogen atom, an alkyl group having 10 or less carbon atoms, a halogenated alkyl group, an aryl group, or a heterocyclic group, and M represents Li, Na, K, NH ₄ , Ag. Indicates one of these.)
A process for producing a 2-cyano-1,3-diketonate salt represented by:
Acetonitrile and the following chemical formula (2)

(In the formula, R ₁ represents a hydrogen atom, an alkyl group having 10 or less carbon atoms, a halogenated alkyl group, an aryl group, or a heterocyclic group, and R ₃ represents an alkyl group having 6 or less carbon atoms. )
A carboxylic acid ester represented by the following chemical formula (3)

(In the formula, R ₄ represents an alkyl group having 6 or less carbon atoms, and M ′ represents Li, Na, or K.)
Is reacted with an alkali metal alkoxide represented by the following chemical formula (4):

(In the formula, R ₁ represents a hydrogen atom, an alkyl group having 10 or less carbon atoms, a halogenated alkyl group, an aryl group, or a heterocyclic group, and M ′ represents Li, Na, or K.)
A first step of producing an α-cyanoketone alkali metal salt represented by:
The α-cyanoketone alkali metal salt represented by the chemical formula (4) and the following chemical formula (5)

(In the formula, R ₂ represents a hydrogen atom, an alkyl group having 10 or less carbon atoms, a halogenated alkyl group, an aryl group, or a heterocyclic group, and X represents an R ₂ COO group, a chlorine atom, or a bromine atom. .)
Is reacted with a carboxylic acid anhydride or a carboxylic acid halide represented by the following chemical formula (6):

(In the formula, R ₁ and R ₂ represent a hydrogen atom, an alkyl group having 10 or less carbon atoms, a halogenated alkyl group, an aryl group, or a heterocyclic group.)
A second step of producing 2-cyano-1,3-diketone represented by
And a third step of reacting the 2-cyano-1,3-diketone represented by the chemical formula (6) with an alkali metal salt, alkali metal, ammonia or silver salt. , 3-Production of diketonate salt. Instead of the second step and the third step,
In the presence of the first base, the α-cyanoketone alkali metal salt represented by the chemical formula (4) is reacted with the carboxylic acid anhydride or carboxylic acid halide represented by the chemical formula (5) to obtain the following chemical formula (7).

(Wherein R ₁ and R ₂ represent a hydrogen atom, an alkyl group having 10 or less carbon atoms, a halogenated alkyl group, an aryl group, or a heterocyclic group, and B represents a first base.)
A fourth step of producing a salt represented by:
The fifth step of reacting the salt represented by the chemical formula (7) with a second base or alkali metal having a pKa of a conjugate acid larger than that of the first base. Of 2-cyano-1,3-diketonate salt.   The method for producing a 2-cyano-1,3-diketonate salt according to claim 2, wherein the first base is triethylamine. Instead of the second step and the third step,
In the presence of any one of LiH, NaH, and KH, the α-cyanoketone alkali metal salt represented by the chemical formula (4) is reacted with the carboxylic acid anhydride or carboxylic acid halide represented by the chemical formula (5). The process for producing a 2-cyano-1,3-diketonate salt according to claim 1, comprising six steps. An ionic liquid comprising a cationic component and an anionic component,
The cation component is an organic cation, and the anion component includes a chemical structure represented by the following chemical formula (8).
In the formula, R ₁ and R ₂ are any of CH ₃ , CH ₂ CH ₃ , CH ₂ CH ₂ CH ₃ , C (CH ₃ ) ₃ , CF ₃ , CF ₂ CF ₃ , and CF ₂ CF ₂ CF ₃ . It is .

6. The ionic liquid according to claim 5 , wherein the anion component is a 3-cyano-1,1,1,5,5,5-hexafluoroacetylacetonate anion represented by the following chemical formula (9).

The ionic liquid according to claim 5 , wherein the anion component is a 3-cyano-1,1,1-trifluoroacetylacetonate anion represented by the following chemical formula (10).

The ionic liquid according to claim 5, wherein the cation component is at least one selected from the group represented by the following chemical formula (11).
In the formula, R ₁ to R ₄ is a hydrogen atom, an alkyl group having 20 or less carbon atoms, an alkoxyalkyl group, a trialkylsilyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group, R ′ _{1 to} R ′ ₁₀ represent a hydrogen atom, an alkyl group having 10 or less carbon atoms, an alkoxyalkyl group, a trialkylsilylalkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group.

The ionic liquid according to claim 5, which has a structure represented by the following chemical formula (12).

The ionic liquid according to claim 5, which has a structure represented by the following chemical formula (13).

The ionic liquid according to claim 5, which has a structure represented by the following chemical formula (14).

The ionic liquid according to claim 5, which has a structure represented by the following chemical formula (15).