JP4924034B2 - Ionic liquid-supported crown compound - Google Patents

Description

  The present invention relates to a novel ionic liquid-supported crown compound that can be recovered and reused.

  An ionic liquid is also called a room temperature molten salt, and has properties such as heat resistance, a wide liquid temperature range, almost no vapor pressure, non-volatility, low viscosity, and high ionic conductivity. .

  An ionic liquid having such characteristics is expected to be applied to a wide range of fields, for example, an environment-friendly reaction solvent for green chemistry, and an electrolyte solution in an electrochemical device field. .

  On the other hand, an organic solvent usually used as a reaction solvent for various synthesis reactions is volatile, and the gas is harmful to the human body and causes pollution and fire. Furthermore, these organic solvents have problems such as causing environmental pollution because they are hardly reused after the reaction and are discarded.

  In order to overcome these problems, many attempts have been made to use ionic liquids as environmentally conscious reaction solvents. Since ionic liquids have almost no vapor pressure and are non-volatile, they are not flammable and flammable, are easy to handle, and are difficult to dissolve in water or organic solvents with low polarity. If various reactions are performed using the ionic liquid as a reaction solvent by using properties, the ionic liquid can be recovered and reused by extracting, for example, products and by-products from the reaction system with water or an organic solvent. It becomes possible to do.

  On the other hand, for example, crown ethers such as 18-crown-6 are widely used as phase transfer catalysts in various reactions such as nucleophilic substitution reactions, but these crown ethers are expensive catalysts and are also used for reaction. Even if it is used as a catalyst, it is difficult to recover, so that there is a problem that it is expensive to carry out a reaction using these crown ethers as a catalyst.

  Under such circumstances, it is desired to develop a new catalyst that has a catalytic action of crown ether and that can be recovered and reused after various reactions.

  The present invention relates to a novel ionic liquid-supported crown compound that can be used as a catalyst that can be recovered and reused.

The present invention has been made for the purpose of solving the above-mentioned problems, and has the general formula [I].

(In the formula, T ₁ represents a linear alkylene group having 1 to 4 carbon atoms, R ³⁸ represents an alkyl group having 1 to 6 carbon atoms or an aralkyl group having 7 to 11 carbon atoms , and R ³⁹ represents a hydrogen atom or It represents an alkyl group having 1 to 6 carbon atoms, X ₁ ⁻ represents a counter anion, and n represents an integer of 1 to 3) .

That is, the inventors have conducted extensive research to achieve the above object, and as a result, the organic synthesis reaction catalyst of the present invention contains an ionic liquid and a crown compound in the molecule. It has been found that it has a catalytic activity such as crown ether such as 6 and can be easily recovered from the reaction system, regenerated, and further reused. Thus, the present invention has been completed.

  When the ionic liquid-supported crown compound of the present invention is used as a catalyst, it is difficult to recover and reuse it from the reaction system despite the fact that a crown compound such as 18-crown-6 is expensive. Since it has an ionic liquid and a crown compound in the molecule without having a point, it has a catalytic action like crown ether, can be recovered efficiently like an ionic liquid, and the recovered catalytic activity Since it can be easily reproduced, it can be reused repeatedly.

In the general formula [1], a group derived from a crown compound represented by R ¹ is derived from a macrocyclic polyether containing a hetero atom such as an oxygen atom, a sulfur atom, or a nitrogen atom. Examples include a group derived from a crown compound having a crown-4 skeleton, a 15-crown-5 skeleton, an 18-crown-6 skeleton, a 21-crown-7 skeleton, and a 24-crown-8 skeleton. Formula [2]

{Wherein R ^{3 to} R ⁸ , m R ⁹ and m R ¹⁰ are each independently a bond bonded to T ₁ in the general formula [1], a hydrogen atom, an alkyl group, Formula [3]

Wherein R ¹¹ represents a hydroxy group, an alkoxy group, an aralkyloxy group or an acyloxy group, a general formula [4]

(Wherein R ¹² and R ¹³ each independently represents a hydrogen atom, a hydroxy group, an alkoxy group or an acyloxy group, except that both R ¹² and R ¹³ are hydrogen atoms). Group or general formula [5]

[Wherein R ¹⁴ represents a hydrogen atom, a hydroxy group, an alkyl group, an alkoxy group, an aryl group or an aryloxy group optionally having an alkyl group as a substituent, or a group represented by the general formula [6]

(Wherein R ¹⁵ and R ¹⁶ each independently represents an alkyl group). And A _{1 to} A ₃ and m A ₄ are each independently an oxygen atom, a sulfur atom or a general formula [7].

(In the formula, R ¹⁷ represents a bond bonded to T ₁ in the general formula [1], a hydrogen atom, an alkyl group, an alkylsulfonyl group, an aryl group which may have an alkyl group as a substituent, or benzenesulfonyl. Represents a group or a heterocyclic group). However, among the cases where any one of R ^{3 to} R ⁸ , m R ⁹ , m R ¹⁰ , and A _{1 to} A ₃ and m A ₄ is a group represented by the general formula [7] Only _one bond is bonded to T ₁ in the general formula [1]. M represents an integer of 1 to 5, R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁷ and R ⁸ , and R ⁹ and R ¹⁰ are each independently a cyclohexane ring together with adjacent carbons. , A benzene ring or a naphthalene ring may be formed. The cyclohexane ring, benzene ring and naphthalene ring may each independently have an alkyl group, an alkenyl group, an acyl group, an acyloxy group, an alkoxycarbonyl group, a morpholinylmethyl group or a decahydronaphthyl group as a substituent. . } Is shown.

In the above, “provided that any one of R ^{3 to} R ⁸ , m R ⁹ , m R ¹⁰ , and A _{1 to} A ₃ and m A ₄ is represented by the general formula [7] , Only _one is a bond that binds to T ₁ in the general formula [1]. ”That is, the bond that binds to T ₁ in the general formula [1] is In the general formula [2], there is only one, and among the groups derived from the crown compound represented by the general formula [2], R ^{3 to} R ⁸ , m R ^{9 s} and m R ^{10 s.} Or R ^{17 represented} by the general formula [7], and the group containing the same corresponds to one of A _{1 to} A ₃ and m A ₄ . Specific examples of the group derived from a crown compound include, for example, the general formula [8].

{Wherein R ^{18 to} R ²² , n R ²³ and n R ²⁴ each independently represent a hydrogen atom, an alkyl group, or a general formula [3].

Wherein R ¹¹ represents a hydroxy group, an alkoxy group, an aralkyloxy group or an acyloxy group, a general formula [4]

(Wherein R ¹² and R ¹³ each independently represents a hydrogen atom, a hydroxy group, an alkoxy group or an acyloxy group, except that both R ¹² and R ¹³ are hydrogen atoms). Group or general formula [5]

[Wherein R ¹⁴ represents a hydrogen atom, a hydroxy group, an alkyl group, an alkoxy group, an aryl group or an aryloxy group optionally having an alkyl group as a substituent, or a group represented by the general formula [6]

(Wherein R ¹⁵ and R ¹⁶ each independently represents an alkyl group). And A _{5 to} A ₇ and n A ₈ are each independently an oxygen atom, a sulfur atom or the general formula [9].

(Wherein R ²⁵ represents a hydrogen atom, an alkyl group, an alkylsulfonyl group, an aryl group which may have an alkyl group as a substituent, a benzenesulfonyl group or a heterocyclic group). , N represents an integer of 1-5. R ¹⁸ and R ¹⁹ , R ²¹ and R ²² , and R ²³ and R ²⁴ may each independently form a cyclohexane ring, a benzene ring, or a naphthalene ring together with adjacent carbons. The cyclohexane ring, benzene ring and naphthalene ring may each independently have an alkyl group, an alkenyl group, an acyl group, an acyloxy group, an alkoxycarbonyl group, a morpholinylmethyl group or a decahydronaphthyl group as a substituent. . } Or a general formula [10]

{In the formula, R ^{26 to} R ³¹ , p R ³² and p R ³³ each independently represent a hydrogen atom, an alkyl group, a general formula [3]

Wherein R ¹¹ represents a hydroxy group, an alkoxy group, an aralkyloxy group or an acyloxy group, a general formula [4]

(Wherein R ¹² and R ¹³ each independently represents a hydrogen atom, a hydroxy group, an alkoxy group or an acyloxy group, except that both R ¹² and R ¹³ are hydrogen atoms). Group or general formula [5]

[Wherein R ¹⁴ represents a hydrogen atom, a hydroxy group, an alkyl group, an alkoxy group, an aryl group or an aryloxy group optionally having an alkyl group as a substituent, or a group represented by the general formula [6]

(Wherein R ¹⁵ and R ¹⁶ each independently represents an alkyl group). And A ₉ , A ₁₀ and p A ₁₁ are each independently an oxygen atom, a sulfur atom or the general formula [9]

(Wherein R ²⁵ represents a hydrogen atom, an alkyl group, an alkylsulfonyl group, an aryl group which may have an alkyl group as a substituent, a benzenesulfonyl group or a heterocyclic group). , P represents an integer of 1 to 5. R ²⁶ and R ²⁷ , R ²⁸ and R ²⁹ , R ³⁰ and R ³¹ , and R ³² and R ³³ each independently form a cyclohexane ring, a benzene ring or a naphthalene ring together with adjacent carbons. May be. The cyclohexane ring, benzene ring and naphthalene ring may each independently have an alkyl group, an alkenyl group, an acyl group, an acyloxy group, an alkoxycarbonyl group, a morpholinylmethyl group or a decahydronaphthyl group as a substituent. . } Is shown.

Examples of the group derived from the ionic liquid represented by R ² include the general formula [11].

( ^Wherein R ^{34q +} represents a quaternary ammonium ion or quaternary phosphonium ion, q X ₁ ⁻ represents a counter anion, and q represents 1 or 2). Can be mentioned.

In the general formula [1], the alkylene chain having 1 to 8 carbon atoms represented by T ₁ is usually a linear alkyl group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms. Examples include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, and the like. Among these, a methylene group, an ethylene group, and the like are preferable.

The alkyl groups represented by R ^{3 to} R ¹⁰ in the general formula [2], R ^{18 to} R ²⁴ in the general formula [8], and R ^{26 to} R ³³ in the general formula [10] are Any of a chain, a branched chain, and a ring may be used, and usually one having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, specifically, for example, methyl group, ethyl group, n-propyl group, isopropyl group , N-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, sec-pentyl group, tert-pentyl group, neopentyl group, n-hexyl group, isohexyl group, sec- Examples include hexyl group, tert-hexyl group, neohexyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and the like.

In the general formulas [3] to [5], the alkoxy group represented by R ^{11 to} R ¹⁴ may be linear, branched or cyclic, and usually has 1 to 6 carbon atoms, preferably 1 And specific examples include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentyl. Oxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, neopentyloxy group, n-hexyloxy group, isohexyloxy group, sec-hexyloxy group, tert-hexyloxy group, neohexyl Examples thereof include an oxy group, a cyclopropoxy group, a cyclobutoxy group, a cyclopentyloxy group, and a cyclohexyloxy group.

In the general formula [3], as the aralkyloxy group represented by R ¹¹ , those having 7 to 11 carbon atoms are usually mentioned. Specific examples include benzyloxy group, phenethyloxy group, naphthylmethoxy group and the like. Is mentioned.

In the general formulas [3] and [4], the acyloxy group represented by R ^{11 to} R ¹³ usually includes those derived from a carboxylic acid having 2 to 20 carbon atoms. Group, propionyloxy group, butyryloxy group, isobutyryloxy group, valeryloxy group, isovaleryloxy group, pivaloyloxy group, hexanoyloxy group, heptanoyloxy group, octanoyloxy group, nonanoyloxy group, decanoyloxy group, Dodecanoyloxy group, tridecanoyloxy group, tetradecanoyloxy group, pentadecanoyloxy group, hexadecanoyloxy group, heptadecanoyloxy group, octadecanoyloxy group, nonadecanoyloxy group, icosanoyl Examples include oxy group, benzoyloxy group, naphthoyloxy group, etc. It is.

The alkyl group represented by R ^{14 to} R ^{17 in the} general formulas [5] to [7] and R ²⁵ in the general formula [9] may be linear, branched or cyclic, Examples thereof usually include those having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms. Specifically, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group Tert-butyl group, n-pentyl group, isopentyl group, sec-pentyl group, tert-pentyl group, neopentyl group, n-hexyl group, isohexyl group, sec-hexyl group, tert-hexyl group, neohexyl group, cyclopropyl Group, cyclobutyl group, cyclopentyl group, cyclohexyl group and the like.

R ¹⁴ in the general formula [5], R ¹⁷ in the general formula [7] and R ²⁵ in the general formula [9] may be substituted with an aryl group which may have an alkyl group. As an aryl group, a C6-C10 thing is normally mentioned, Specifically, a phenyl group, a naphthyl group, etc. are mentioned, for example.

  Examples of the alkyl group exemplified as the substituent include those having 1 to 3 carbon atoms. Specific examples include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.

  Preferable specific examples of the aryl group having an alkyl group as a substituent include, for example, a tolyl group, a xylyl group, and a cumenyl group.

In the general formula [5], the aryloxy group of the aryloxy group which may have an alkyl group as the substituent represented by R ¹⁴ usually includes those having 6 to 10 carbon atoms. Examples include phenoxy group and naphthoxy group.

  Examples of the alkyl group exemplified as the substituent include those having 1 to 3 carbon atoms. Specific examples include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.

  Preferable specific examples of the aryloxy group having an alkyl group as a substituent include, for example, 2-methylphenoxy group, 3-methylphenoxy group, 4-methylphenoxy group, 2,4-dimethylphenoxy group, 3,5-dimethylphenoxy group. Groups, etc., among which, for example, 4-methylphenoxy group, 2,4-dimethylphenoxy group and the like are preferable.

As the alkylsulfonyl group represented by R ¹⁷ in the general formula [7] and R ²⁵ in the general formula [9], the —OH group in the sulfonic acid group is substituted with an alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group include R ^{3 to} R ¹⁰ in the general formula [2], R ^{18 to} R ²⁴ in the general formula [8], and the general formula [10]. kicking include the same examples of the alkyl group represented by ^R 26 ^{to R 33.}

The benzenesulfonyl group optionally having an alkyl group as the substituent represented by R ¹⁷ in the general formula [7] and R ²⁵ in the general formula [9] is an aromatic ring in the benzenesulfonyl group. Examples thereof include those in which 1 to 5, preferably 1 to 2 hydrogen atoms are substituted with an alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group include R ³ to R ^{3 in} the above general formula [2]. Examples of R ¹⁰ are the same as those exemplified for the alkyl groups represented by R ^{18 to} R ²⁴ in the general formula [8] and R ^{26 to} R ³³ in the general formula [10].

  Preferable specific examples of the benzenesulfonyl group having an alkyl group as a substituent include, for example, a toluenesulfonyl group, a xylenesulfonyl group, a cumenesulfonyl group and the like.

Examples of the heterocyclic group represented by R ¹⁷ in the general formula [7] and R ²⁵ in the general formula [9] include one or more heteroatoms such as a nitrogen atom, a sulfur atom, and an oxygen atom, preferably 1 to 3 may be mentioned, and it may be monocyclic or polycyclic, and specific examples include thienyl group, quinolyl group, isoquinolyl group, pyridyl group, thiazolyl group, furfuryl group, imidazolyl group and the like.

  M in the general formula [2], n in the general formula [8], and p in the general formula [10] are usually an integer of 1 to 5, preferably 1 to 3, more preferably 3. .

R ³ and R ^{4 in} the general formula [2], R ⁵ and R ⁶ , R ⁷ and R ^{8 and} m R ⁹ and R ¹⁰ , R ¹⁸ and R ¹⁹ in the general formula [8], R ²¹ and R ²² , n R ²³ and R ²⁴ , and R ²⁶ and R ²⁷ , R ²⁸ and R ²⁹ , R ³⁰ and R ³¹ , and p R ³² and R ³³ in the general formula [10] are A cyclohexane ring, a benzene ring and a naphthalene ring may be formed together with carbons adjacent to each other.

  The cyclohexane ring, benzene ring and naphthalene ring may further have a substituent. Examples of the substituent include an alkyl group, an alkenyl group, an acyl group, an acyloxy group, an alkoxycarbonyl group, a morpholinylmethyl group, a decahydro group. A naphthyl group etc. are mentioned.

The alkyl group mentioned as these substituents may be linear, branched or cyclic, and usually has 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms. Examples of alkyl groups represented by R ^{3 to} R ¹⁰ in the general formula [2], R ^{18 to} R ²⁴ in the general formula [8], and R ^{26 to} R ³³ in the general formula [10] The same thing is mentioned.

  The alkenyl group mentioned as the substituent may be linear, branched or cyclic, and usually includes those having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms. Vinyl group, allyl group, 1-propenyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-methylallyl group, 2-methylallyl group, 1-methyl-1-propenyl group, 2 -Methyl-1-propenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-methyl-1-butenyl group, 2-methyl-1-butenyl group, 3-methyl- 1-butenyl group, 1,1-dimethyl-1-propenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, 3-methyl-3-pentenyl group, Cyclopropenyl group, cyclobutenyl group, cyclopentenyl group, cyclohexenyl group, etc. Can be mentioned.

  Examples of the acyl group exemplified as the substituent include those usually derived from a carboxylic acid having 2 to 20 carbon atoms, specifically, for example, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, Pivaloyl group, hexanoyl group, heptanoyl group, octanoyl group, nonanoyl group, decanoyl group, dodecanoyl group, tridecanoyl group, tetradecanoyl group, pentadecanoyl group, hexadecanoyl group, heptadecanoyl group, octadecanoyl group, nonadecanoyl group, Examples include icosanoyl group, benzoyl group, naphthoyl group and the like.

Examples of the acyloxy group exemplified as the substituent include those usually derived from a carboxylic acid having 2 to 20 carbon atoms, and specifically, for example, R ^{11 to} R ^{13 in the} above general formulas [3] and [4]. The same thing as the illustration of the acyloxy group shown by these is mentioned.

Examples of the alkoxycarbonyl group exemplified as the substituent include those in which a hydrogen atom of a carboxylic acid is substituted with an alkyl group having 1 to 6 carbon atoms. The alkyl group includes R in the above general formula [2]. Examples of the alkyl group represented by ^{3 to} R ¹⁰ , R ^{18 to} R ²⁴ in the general formula [8] and R ^{26 to} R ³³ in the general formula [10] are the same.

In the general formula [8], it is preferable that R ^{18 to} R ²² , n R ²³ and n R ²⁴ are all hydrogen atoms.

A _{5 to} A ₇ and n A ₈ are preferably all oxygen atoms.

In the general formula [10], it is preferable that R ^{26 to} R ³¹ , p R ³² and p R ³³ are all hydrogen atoms.

A ₉ , A ₁₀ and p A ₁₁ are all preferably oxygen atoms.

In the general formula [1], specific examples of the group derived from the crown compound represented by R ¹ include a crown compound such as a macrocyclic polyether containing a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom. For example, “Chemistry of Crown Ether and Cryptand—Synthetic Multidentate Macrocyclic Compounds” (co-edited by RMIzatt / JJChristensen, translated by Toshiyuki Shono, Shozo Yanagida, and Keiichi Kimura), Table 2, Examples include those derived from the crown compounds described in 1 “Synthesis of Crown Compounds” (see pages 63 to 107).

  Preferable specific examples of the group derived from the crown compound represented by the general formula [8] include, for example, the general formula [12].

(Wherein A _{5 to} A ₈ are the same as defined above), a group derived from a 12-crown-4 skeleton represented by the general formula [13]

(Wherein A _{5 to} A ₇ and two A ₈ are the same as defined above), a group derived from a 15-crown-5 skeleton represented by the general formula [14]

(Wherein A _{5 to} A ₇ and three A ₈ are the same as above), a group derived from an 18-crown-6 skeleton represented by the general formula [15]

(Wherein A _{5 to} A ₇ and four A ₈ are the same as defined above), a group derived from a 21-crown-7 skeleton represented by the general formula [16]

(Wherein A _{5 to} A ₇ and 5 A ₈ are the same as above), a group derived from a 24-crown-8 skeleton, etc.

A group represented by the formula (equivalent to the general formula [12], wherein A _{5 to} A ₈ are oxygen atoms), the formula [18]

A group represented by formula (19): in general formula [13], A _{5 to} A ₇ and two A ₈ are oxygen atoms;

(In the general formula [14], corresponding to those in which A _{5 to} A ₇ and three A ₈ are oxygen atoms), the formula [20]

(In General Formula [14], A ₅ and one A ₈ are nitrogen atoms, and A ₆ , A ₇ and two A ₈ are oxygen atoms.), Formula [21]

(In General Formula [14], A ₆ and one A ₈ are nitrogen atoms, and A ₅ , A ₇ and two A ₈ are oxygen atoms.), Formula [22]

(In the general formula [14], A ₇ and one A ₈ are nitrogen atoms, and A ₅ , A ₆ and two A ₈ are oxygen atoms). Among these, a group represented by the formula [19] is more preferable.

Preferable specific examples of the group derived from the crown compound represented by the general formula [10] include, for example, the general formula [23].

(Wherein A _{9 to} A ₁₁ are the same as defined above), a group derived from an aza-12-crown-4 skeleton represented by the general formula [24]

(Wherein A ₉ , A ₁₀ and two A ₁₁ are the same as defined above), a group derived from an aza-15-crown-5 skeleton represented by the general formula [25]

(Wherein A ₉ , A ₁₀ and three A ₁₁ are the same as above), a group derived from an aza-18-crown-6 skeleton represented by the general formula [26]

(Wherein A ₉ , A ₁₀ and four A ₁₁ are the same as above), a group derived from an aza-21-crown-7 skeleton represented by the general formula [27]

(Wherein A ₉ , A ₁₀ and 5 A ₁₁ are the same as above), a group derived from an aza-24-crown-8 skeleton represented by the formula [28]

A group represented by formula (29) (corresponding to A _{9 to} A ₁₁ being an oxygen atom in general formula [23]), formula [29]

(In the general formula [24], A ₉ , A ₁₀ and two A ₁₁ are oxygen atoms), and the formula [30]

(In the general formula [25], A ₉ , A ₁₀ and three A ₁₁ are each an oxygen atom) and the like are preferred, and in particular, a group represented by the formula [30] Is more preferable.

In the general formula [11], ^examples of the q-valent quaternary ammonium ion ^represented by R ^{34q +} include, for example, the general formula [31].

(Wherein R ^{35 to} R ³⁷ each independently represents a hydrogen atom, an alkyl group, an aralkyl group or an alkenyl group, except that R ^{35 to} R ³⁷ are both hydrogen atoms). And general formula [32]

Wherein R ³⁸ represents an alkyl group or an aralkyl group, and R ³⁹ represents a hydrogen atom or an alkyl group, a general formula [33]

(Wherein k R ^{40 s} each independently represents an alkyl group, k represents an integer of 1 to 5), a monovalent quaternary ammonium ion such as a group represented by the general formula [ 34]

(Wherein, R ⁴¹ represents an alkyl group) and a divalent quaternary ammonium ion such as a group represented by

^Examples of the q-valent quaternary phosphonium ion represented by R ^{34q +} include a compound represented by the general formula [35].

(Wherein, R ^{35 to} R ³⁷ are the same as above) and monovalent quaternary phosphonium ions such as a group represented by

In the general formulas [31] to [35], the alkyl group represented by R ^{35 to} R ⁴¹ may be linear, branched or cyclic, and usually has 1 to 6 carbon atoms, preferably 1 -3, specifically, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group , Isopentyl group, sec-pentyl group, tert-pentyl group, neopentyl group, n-hexyl group, isohexyl group, sec-hexyl group, tert-hexyl group, neohexyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group Etc.

In the general formulas [31], [32] and [35], examples of the aralkyl group represented by R ^{35 to} R ³⁸ include those usually having 7 to 11 carbon atoms. Phenethyl group, 1-phenylethyl group, 2-phenylpropyl group, 3-phenylpropyl group, phenylbutyl group, 1-methyl-3-phenylpropyl group, naphthylmethyl group and the like.

In the general formulas [31] and [35], the alkenyl group represented by R ^{35 to} R ³⁷ may be linear, branched or cyclic, and usually has 2 to 20 carbon atoms. Specifically, for example, vinyl group, allyl group, 1-propenyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-methylallyl group, 2-methylallyl group, 1- Methyl-1-propenyl group, 2-methyl-1-propenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-methyl-1-butenyl group, 2-methyl-1 -Butenyl group, 3-methyl-1-butenyl group, 1,1-dimethyl-1-propenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, 3 -Methyl-3-pentenyl group, heptenyl group, octenyl group, noneryl group, decenyl group, undecenyl group Group, dodecenyl group, tridecenyl group, tetradecenyl group, pentadecenyl group, hexadecenyl group, heptadecenyl group, 9-octadecenyl group, nonadecenyl group, icocenyl group, cyclopropenyl group, cyclobutenyl group, cyclopentenyl group, cyclohexenyl group, etc. .

  In the general formula [33], k is usually an integer of 1 to 5, preferably 1 or 2.

In the general formula [11], examples of the counter anion represented by X ₁ ⁻ include a halogen atom, hexafluorophosphoric acid, (HPF ₆ ), tetrachloroaluminic acid (HA1Cl ₄ ), and the general formula [36].

(Wherein R ⁴² represents a haloalkyl group), an imidic acid represented by the general formula [37]

(Wherein R ⁴³ represents a haloalkyl group), a carbon acid represented by the general formula [38]

(Wherein R ⁴⁴ represents a fluorine atom, a phenyl group or a cyano group optionally having a haloalkyl group as a substituent), boric acid represented by the general formula [39]

(Wherein R ⁴⁵ represents an alkyl group, a haloalkyl group, or a phenyl group optionally having an alkyl group or a halogen atom as a substituent) or a general formula [40]

(In the formula, R ⁴⁶ represents an alkyl group, a haloalkyl group, or a phenyl group which may have an alkyl group or a halogen atom as a substituent.)

Examples of the halogen atom exemplified as the counter anion represented by X ₁ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

In the general formulas [36], [37], [39] and [40], the haloalkyl group represented by R ⁴² , R ⁴³ , R ⁴⁵ and R ⁴⁶ is linear, branched or cyclic. Any may be sufficient, Usually, one or all of the hydrogen atoms of the alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, are substituted with halogen atoms (for example, fluorine atom, chlorine atom, bromine atom, iodine atom, etc.). Specifically, for example, fluoromethyl group, chloromethyl group, bromomethyl group, iodomethyl group, difluoromethyl group, trifluoromethyl group, trichloromethyl group, tribromomethyl group, triiodomethyl group, trifluoro Ethyl group, trichloroethyl group, tribromoethyl group, triiodoethyl group, pentafluoroethyl group, pentachloroethyl group, pentabromoethyl Group, pentaiodoethyl group, trifluoropropyl group, heptafluoropropyl group, heptachloropropyl group, heptabromopropyl group, heptaiodopropyl group, trifluorobutyl group, nonafluorobutyl group, nonachlorobutyl group, nonabromobutyl group Nonaiodobutyl group, trifluoropentyl group, undecafluoropentyl group, undecachloropentyl group, undecabromopentyl group, undecaiodopentyl group, trifluorohexyl group, tridecafluorohexyl group, tridecachlorohexyl group, Tridecabromohexyl group, tridecaiodohexyl group, trifluoroheptyl group, pentadecafluoroheptyl group, pentadecachloroheptyl group, pentadecabromoheptyl group, pentadecaiodoheptyl group, trifluoro Octyl group, heptadecafluorooctyl group, heptadecachlorooctyl group, heptadecabromooctyl group, heptadecaiodooctyl group, trifluorononyl group, nonadecafluorononyl group, nonadecachlorononyl group, nonadecabromononyl group, Nonadecaiodononyl group, trifluorodecyl group, perfluorodecyl group, perchlorodecyl group, perbromodecyl group, periododecyl group, perfluoroundecyl group, perchloroundecyl group, perbromoundecyl group, perbromodecyl group Iodoundecyl group, perfluorododecyl group, perchlorododecyl group, perbromododecyl group, periodododecyl group, perfluorotridecyl group, perchlorotridecyl group, perbromotridecyl group, periodotridecyl group, periodotridecyl group Fluorotetradecyl group, par Chlorotetradecyl group, perbromotetradecyl group, periodotetradecyl group, perfluoropentadecyl group, perchloropentadecyl group, perbromopentadecyl group, periodopentadecyl group, perfluorohexadecyl group, perchlorohexadecyl group Group, perbromohexadecyl group, periodohexadecyl group, perfluoroheptadecyl group, perchloroheptadecyl group, perbromoheptadecyl group, periodoheptadecyl group, perfluorooctadecyl group, perchlorooctadecyl group, perbromooctadecyl group Periodooctadecyl group, perfluorononadecyl group, perchlorononadecyl group, perbromononadecyl group, periodononadecyl group, perfluoroicosyl group, perchloroicosyl group, perbromoicosyl group, Yodoikoshiru group, perfluorocyclohexyl group, perchlorethylene cyclohexyl group, perbromooctyl cyclohexyl group, perfluoro-iodo cyclohexyl group.

In the general formula [38], the phenyl group optionally having a haloalkyl group as a substituent represented by R ⁴⁴ is, for example, a phenyl group, 1 to 5 phenyl groups, preferably 1 to 3 hydrogen atoms. And those in which the atom is substituted with a haloalkyl group.

The haloalkyl group mentioned as these substituents may be linear, branched or cyclic, and usually some or all of the hydrogen atoms of the alkyl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms are halogen. Examples thereof include those substituted with atoms (for example, fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), specifically, for example, the general formulas [36], [37], [39] and [40] described above. Examples of the haloalkyl group represented by R ⁴² , R ⁴³ , R ⁴⁵ and R ⁴⁶ in FIG.

In the general formulas [39] and [40], the alkyl group represented by R ⁴⁵ and R ⁴⁶ may be linear, branched or cyclic, and usually has 1 to 20 carbon atoms, preferably 1 -10, and specifically, for example, R ^{3 to} R ¹⁰ in the general formula [2], R ^{18 to} R ²⁴ in the general formula [8], and the general formula [10]. The same as the examples of the alkyl group represented by R ^{26 to} R ³³ in the formula, n-heptyl group, isoheptyl group, sec-heptyl group, tert-heptyl group, neoheptyl group, n-octyl group, isooctyl group, sec -Octyl, tert-octyl, neooctyl, n-nonyl, isononyl, sec-nonyl, tert-nonyl, neononyl, n-decyl, isodecyl, sec-decyl, tert-decyl , Neodecyl group, n-undecyl group, isotope Ndecyl group, sec-undecyl group, tert-undecyl group, neoundecyl group, n-dodecyl group, isododecyl group, sec-dodecyl group, tert-dodecyl group, neododecyl group, n-tridecyl group, isotridecyl group, sec-tridecyl group, tert-tridecyl group, neotridecyl group, n-tetradecyl group, isotetradecyl group, sec-tetradecyl group, tert-tetradecyl group, neotetradecyl group, n-pentadecyl group, isopentadecyl group, sec-pentadecyl group, tert- Pentadecyl group, neopentadecyl group, n-hexadecyl group, isohexadecyl group, sec-hexadecyl group, tert-hexadecyl group, neohexadecyl group, n-heptadecyl group, isoheptadecyl group, sec-heptadecyl group, tert-heptadecyl group Group, neoheptadecyl group, n-octadecyl group, isooctadecyl group, sec-octadecyl group, tert- Tadecyl group, neooctadecyl group, n-nonadecyl group, isononadecyl group, sec-nonadecyl group, tert-nonadecyl group, neononadecyl group, n-icosyl group, isoicosyl group, sec-icosyl group, tert-icosyl group, neoicosyl group, cyclo A propyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and the like can be given.

In the general formulas [39] and [40], examples of the phenyl group optionally having an alkyl group or a halogen atom as the substituent represented by R ⁴⁵ and R ⁴⁶ include a phenyl group, Examples include 5 or preferably 1 to 3 hydrogen atoms substituted with an alkyl group or a halogen atom.

The alkyl group exemplified as these substituents may be linear, branched or cyclic, and usually includes those having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. In the general formulas [39] and [40], the same alkyl groups represented by R ⁴⁵ and R ⁴⁶ are exemplified.

  Examples of the halogen atom exemplified as these substituents include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

^Examples of the group derived from the ionic liquid ^represented by R ^{34q + represented} by the general formula [11] include, for example, a group derived from an imidazolium cation represented by the general formula [32] and a pyridinium cation represented by the general formula [33]. A group derived from imidazolium cation represented by the general formula [32] is more preferable.

  Preferable specific examples of the group derived from the quaternary ammonium cation represented by the general formula [31] include, for example, triethylammonium ion, tri-n-propylammonium ion, tri-n-butylammonium ion, and tri-n-pentylammonium. Ion, tri-n-hexyl ammonium ion, tri-n-heptyl ammonium ion, tri-n-octyl ammonium ion, tri-n-nonyl ammonium ion, tri-n-decyl ammonium ion, tri-n-undecyl ammonium ion , Trilauryl (dodecyl) ammonium ion, tri-n-tridecyl ammonium ion, trimyristyl (tetradecyl) ammonium ion, tri-n-pentadecyl ammonium ion, tricetyl ammonium ion, tri-n-heptadecyl ammonium ion, diocta Silmethylammonium ion, didecylmethylammonium ion, dinonylmethylammonium ion, dioctylethylammonium ion, diheptylpentylammonium ion, diheptylpropylammonium ion, diheptylmethylammonium ion, dihexylbutylammonium ion, dihexylethylammonium ion, Nonyl dipentyl ammonium ion, hexyl dipentyl ammonium ion, dipentyl butyl ammonium ion, dipentyl methyl ammonium ion, octyl dibutyl ammonium ion, hexyl dibutyl ammonium ion, tridecyl dipropyl ammonium ion, undecyl dipropyl ammonium ion, heptyl dipropyl ammonium ion, Hexilji Propylammonium ion, dipropylmethylammonium ion, tetradecyldiethylammonium ion, octyldiethylammonium ion, octadecyldimethylammonium ion, heptadecyldimethylammonium ion, hexadecyldimethylammonium ion, dodecyldimethylammonium ion, decyldimethylammonium ion, nonyl Dimethylammonium ion, octyldimethylammonium ion, hexyldimethylammonium ion, ethyldimethylammonium ion, undecylbutylpropylammonium ion, undecylbutylethylammonium ion, undecylpropylethylammonium ion, nonyloctylethylammonium ion, nonyloctylmethylammoni Ion, nonylhexylbutylammonium ion, nonylhexylmethylammonium ion, nonylpentylmethylammonium ion, nonylbutylmethylammonium ion, octylhexylpentylammonium ion, octylhexylpropylammonium ion, octylhexylmethylammonium ion, octylpentylbutylammonium ion, Octylpentylpropylammonium ion, octylpentylmethylammonium ion, octylbutylpropylammonium ion, octylethylmethylammonium ion, heptylpentylmethylammonium ion, hexylpentylbutylammonium ion, hexylpentylmethylammonium ion, hexylbutylmethylammonium Groups derived from trialkylammonium cations such as ions, pentylbutylpropylammonium ions, such as dialkenylalkylammonium cations such as dioleyl (9-octadecenyl) methylammonium ions, such as benzyldimethylammonium ion, benzyldiethylammonium ion, benzyl Examples include groups derived from quaternary ammonium cations such as groups derived from aralkyl dialkyl ammonium cations such as dipropylammonium ion and benzyldi-n-propylammonium ion.

  Preferred specific examples of the group represented by the general formula [32] include, for example, 3-methylimidazolium ion, 3-ethylimidazolium ion, 3-butylimidazolium ion, 3-pentylimidazolium ion, and 3-hexylimidazolium ion. Alkyl substituted imidazoles such as ions, 3-octylimidazolium ions, 3-decylimidazolium ions, 3-dodecylimidazolium ions, 3-tetradecylimidazolium ions, 3-hexadecylimidazolium ions, 3-octadecylimidazolium ions, etc. Groups derived from a cation, for example, a group derived from an aralkyl-substituted imidazolium cation such as 3-benzylimidazolium ion, 3-phenylpropylimidazolium ion, such as 2,3-dimethylimidazolium ion, 2-methyl-3-ethylimidazole Lithium ion, 2-methyl-3-buty Groups derived from alkyl disubstituted imidazolium cations such as loumidazolium ion, 2-methyl-3-propylimidazolium ion, 2-methyl-3-hexyl imidazolium ion, 2-methyl-3-hexadecylimidazolium ion, etc. Can be mentioned.

  Preferable specific examples of the group represented by the general formula [33] include, for example, pyridinium ion, 3-methylpyridinium ion, 3-ethylpyridinium ion, 4-methylpyridinium ion, 4-ethylpyridinium ion, and 3,4-dimethylpyridinium. And groups derived from pyridinium cations such as ions and 3,5-dimethylpyridinium ions.

  Preferable specific examples of the group represented by the general formula [34] include, for example, N-methyl-4,4′-bipyridinium ion, N-ethyl-4,4′-bipyridinium ion, N-propyl-4,4′- Bipyridinium ion, N-butyl-4,4'-bipyridinium ion, N-pentyl-4,4'-bipyridinium ion, N-hexyl-4,4'-bipyridinium ion, N-heptyl-4,4'-bipyridinium ion N-octyl-4,4'-bipyridinium ion, N-nonyl-4,4'-bipyridinium ion, N-decyl-4,4'-bipyridinium ion, N-undecyl-4,4'-bipyridinium ion, N -Dodecyl-4,4'-bipyridinium ion, N-tridecyl-4,4'-bipyridinium ion, N-tetradecyl-4,4'-bipyridinium ion, N-pentadecyl-4,4'-bipyridinium ion, N-hexadecyl -4,4'-bipyridinium ion, N-heptadecyl-4,4'-bipyridinium ion Derived from N-alkyl-4,4'-bipyridinium cations such as N-octadecyl-4,4'-bipyridinium ion, N-nonadecyl-4,4'-bipyridinium ion, N-icosyl-4,4'-bipyridinium ion And groups derived from 4,4′-bipyridinium cations such as groups derived from N-aralkyl-4,4′-bipyridinium cations such as N-benzyl-4,4′-bipyridinium ions.

  Preferred examples of the group represented by the general formula [35] include, for example, trimethylphosphonium ion, triethylphosphonium ion, tripropylphosphonium ion, tributylphosphonium ion, tripentylphosphonium ion, trihexylphosphonium ion, triheptylphosphonium ion, Octylphosphonium ion, trinonylphosphonium ion, tridecylphosphonium ion, triundecylphosphonium ion, tridodecylphosphonium ion, tri (tridecyl) phosphonium ion, tri (tetradecyl) phosphonium ion, tri (hexadecyl) phosphonium ion, tri (heptadecyl) Phosphonium ion, tri (octadecyl) phosphonium ion, tri (nonadecyl) phosphonium ion Groups derived from trialkylphosphonium cations such as triicosylphosphonium ion, dihexylmethylphosphonium ion, groups derived from dialkenylalkylphosphonium cations such as dioleyl (9-octadecenyl) methylphosphonium ion, such as benzyldimethylphosphonium ion, benzyldiethyl Examples include groups derived from quaternary phosphonium cations such as groups derived from aralkyl dialkylphosphonium cations such as phosphonium ions and benzyldipropylphosphonium ions.

  Preferred specific examples of the imide acid represented by the general formula [36] include, for example, bis (trifluoromethylsulfonyl) imidic acid, bis (pentafluoroethylsulfonyl) imidic acid, bis (heptafluoropropylsulfonyl) imidic acid, bis ( Nonafluorobutylsulfonyl) imidic acid, bis (perfluoropentylsulfonyl) imidic acid, bis (perfluorohexylsulfonyl) imidic acid, bis (perfluoroheptylsulfonyl) imidic acid, bis (perfluorooctylsulfonyl) imidic acid, bis (Trichloromethylsulfonyl) imidic acid, bis (pentachloroethylsulfonyl) imidic acid, bis (heptachloropropylsulfonyl) imidic acid, bis (nonachlorobutylsulfonyl) imidic acid, bis (perchloropentylsulfonyl) i Doic acid, bis (perchlorohexylsulfonyl) imidic acid, bis (perchloroheptylsulfonyl) imidic acid, bis (perchlorooctylsulfonyl) imidic acid, bis (tribromomethylsulfonyl) imidic acid, bis (pentabromoethylsulfonyl) Imido acid, bis (heptabromopropylsulfonyl) imidic acid, bis (nonabromobutylsulfonyl) imidic acid, bis (perbromopentylsulfonyl) imidic acid, bis (perbromohexylsulfonyl) imidic acid, bis (perbromoheptylsulfonyl) Imido acid, bis (perbromooctylsulfonyl) imidic acid, etc. are mentioned. Among them, for example, bis (pentafluoroethylsulfonyl) imidic acid, bis (trifluoromethylsulfonyl) imidic acid, bis (perfluorooctylsulfonyl) ) Such as imide acid.

  Preferable specific examples of the carbon acid represented by the general formula [37] include, for example, tris (trifluoromethylsulfonyl) carbon acid, tris (pentafluoroethylsulfonyl) carbon acid, tris (nonafluoropropylsulfonyl) carbon acid, tris ( Perfluorobutylsulfonyl) carbon acid, tris (perfluoropentylsulfonyl) carbon acid, tris (perfluorohexylsulfonyl) carbon acid, tris (perfluoroheptylsulfonyl) carbon acid, tris (perfluorooctylsulfonyl) carbon acid, tris (Trichloromethylsulfonyl) carbon acid, Tris (pentachloroethylsulfonyl) carbon acid, Tris (nonachloropropylsulfonyl) carbon acid, Tris (perchlorobutylsulfonyl) carbon acid, Tris (perchloropentylsulfonyl) carbon acid Tris (perchlorohexylsulfonyl) carbon acid, tris (perchloroheptylsulfonyl) carbon acid, tris (perchlorooctylsulfonyl) carbon acid, tris (tribromomethylsulfonyl) carbon acid, tris (pentabromoethylsulfonyl) carbon acid, Tris (nonabromopropylsulfonyl) carbon acid, tris (perbromobutylsulfonyl) carbon acid, tris (perbromopentylsulfonyl) carbon acid, tris (perbromohexylsulfonyl) carbon acid, tris (perbromoheptylsulfonyl) carbon acid, Examples include tris (perbromooctylsulfonyl) carbon acid, among which tris (trifluoromethylsulfonyl) carbon acid, tris (pentafluoroethylsulfonyl) carbon acid, and tris (perfluorooctylsulfonyl) carbon acid. Acid, and the like are preferable.

  Preferable specific examples of the boric acid represented by the general formula [38] include, for example, tetrafluoroboric acid, tetrachloroboric acid, tetrabromoboric acid, tetraiodoboric acid, tetracyanoboric acid, tetraphenylboric acid, tetrakis { Examples thereof include bis (triphenylmethyl) phenyl} boric acid, and among them, for example, tetrafluoroboric acid is preferable.

  Preferable specific examples of the sulfonic acid represented by the general formula [39] include alkylsulfonic acids such as methanesulfonic acid, ethanesulfonic acid, and propanesulfonic acid, such as trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, and heptafluoropropane. Sulfonic acid, nonafluorobutanesulfonic acid, perfluoropentanesulfonic acid, perfluorohexanesulfonic acid, perfluoroheptanesulfonic acid, perfluorooctanesulfonic acid, trichloromethanesulfonic acid, pentachloroethanesulfonic acid, heptachloropropanesulfonic acid, nonachloro Butanesulfonic acid, perchloropentanesulfonic acid, perchlorohexanesulfonic acid, perchloroheptanesulfonic acid, perchlorooctanesulfonic acid, tribromomethanesulfone Haloalkylsulfonic acids such as pentabromoethanesulfonic acid, heptabromopropanesulfonic acid, nonabromobutanesulfonic acid, perbromopentanesulfonic acid, perbromohexanesulfonic acid, perbromoheptanesulfonic acid, perbromooctanesulfonic acid, such as benzene Aryl sulfonic acids such as sulfonic acid, for example, alkyl-substituted benzene sulfonic acid such as p-toluenesulfonic acid (tosylic acid), etc. Among them, for example, trifluoromethane sulfonic acid, pentafluoroethane sulfonic acid, nonafluoropropane sulfonic acid, Perfluorooctane sulfonic acid and the like are preferable.

  Preferred specific examples of the carboxylic acid represented by the general formula [40] include alkyl carboxylic acids such as acetic acid, propionic acid, butyric acid, and isobutyric acid, such as perfluoroacetic acid, perfluoropropionic acid, perfluorobutanoic acid, perfluoro. Halogen-substituted alkyl carboxylic acids such as octanoic acid, chloroacetic acid, perchloroacetic acid, perchloropropionic acid, perchlorobutanoic acid, perchlorooctanoic acid, perbromoacetic acid, perbromopropionic acid, perbromobutanoic acid, perbromooctanoic acid, etc. Can be mentioned.

  Examples of the ionic liquid-carrying crown compound represented by the general formula [1] include those represented by the following general formulas [41] to [90].

(Wherein R ^{35 to} R ⁴¹ , T ₁ , A _{5 to} A ₇ , 1 to 5 A ₈ , A ₉ , A ₁₀ , 1 to 5 A ₁₁ , X ₁ and k are the same as above. )
Among these ionic liquid-supported crown compounds, those represented by the general formulas [42], [47], [52], [53], [67], [72], [77] and [82] (in particular, A _{5 to} A ₈ and A _{9 to} A ₁₁ are preferably oxygen atoms.) Among them, one represented by the general formula [52] (especially, A _{5 to} A ₈ is an oxygen atom) Is more preferred).

  Preferred specific examples of the ionic liquid-supported crown compound represented by the general formula [1] include, for example, 1- (methyl-18-crown-6) -3-methyl-3H-imidazol-1-ium chloride, 1- ( Methyl-18-crown-6) -3-methyl-3H-imidazol-1-ium bromide, 1- (methyl-18-crown-6) -3-methyl-3H-imidazol-1-ium iodide, 1- ( Methyl-18-crown-6) -3-methyl-3H-imidazol-1-ium hexafluorophosphate, 1- (methyl-18-crown-6) -3-methyl-3H-imidazol-1-ium tetra Fluoroborate, 1- (methyl-18-crown-6) -3-methyl-3H-imidazol-1-ium trifluoromethanesulfonate, 1- (methyl-18-crown-6) -3-methyl- 3H-imidazol-1-ium tetrachloroaluminate, 1- (methyl-18-crown-6) -3-butyl-3H-imidazol-1-ium chloride, 1- (methyl-1 8-crown-6) -3-butyl-3H-imidazol-1-ium bromide, 1- (methyl-18-crown-6) -3-butyl-3H-imidazol-1-ium iodide, 1- (methyl- 18-crown-6) -3-butyl-3H-imidazol-1-ium hexafluorophosphate, 1- (methyl-18-crown-6) -3-butyl-3H-imidazol-1-ium tetrafluoroborate Acid salt, 1- (methyl-18-crown-6) -3-butyl-3H-imidazol-1-ium trifluoromethanesulfonate, 1- (methyl-18-crown-6) -3-butyl-3H- Imidazole-1-ium tetrachloroaluminate, 1- (methyl-15-crown-5) -3-methyl-3H-imidazol-1-ium chloride, 1- (methyl-15-crown-5) -3- Methyl-3H-imidazol-1-ium bromide, 1- (methyl-15-crown-5) -3-methyl-3H-imidazol-1-ium iodide, 1- (methyl-15-crown-5) -3- Methyl-3H-imidazo Ru-1-ium hexafluorophosphate, 1- (methyl-15-crown-5) -3-methyl-3H-imidazol-1-ium tetrafluoroborate, 1- (methyl-15-crown-5 ) -3-Methyl-3H-imidazol-1-ium trifluoromethanesulfonate, 1- (methyl-15-crown-5) -3-methyl-3H-imidazol-1-ium tetrachloroaluminate, 1- (1-aza-18-crown-6) -3-methyl-3H-imidazol-1-ium chloride, 1- (1-aza-methyl-18-crown-6) -3-methyl-3H-imidazole-1 -Ium bromide, 1- (1-aza-methyl-18-crown-6) -3-methyl-3H-imidazol-1-ium iodide, 1- (1-aza-methyl-18-crown-6) -3 -Methyl-3H-imidazol-1-ium hexafluorophosphate, 1- (1-aza-methyl-18-crown-6) -3-methyl-3H-imidazol-1-ium tetrafluoroborate, 1 -(1-aza-methyl-18-kura -6) -3-Methyl-3H-imidazol-1-ium trifluoromethanesulfonate, 1- (1-aza-methyl-18-crown-6) -3-methyl-3H-imidazol-1-ium tetra Chloroaluminate, 1- (1-aza-methyl-18-crown-6) -3-butyl-3H-imidazol-1-ium chloride, 1- (1-aza-methyl-18-crown-6)- 3-butyl-3H-imidazol-1-ium bromide, 1- (1-aza-methyl-18-crown-6) -3-butyl-3H-imidazol-1-ium iodide, 1- (1-aza-methyl -18-crown-6) -3-butyl-3H-imidazol-1-ium hexafluorophosphate, 1- (1-aza-methyl-18-crown-6) -3-butyl-3H-imidazole-1 -Ium tetrafluoroborate, 1- (1-aza-methyl-18-crown-6) -3-butyl-3H-imidazol-1-ium trifluoromethanesulfonate, 1- (1-aza-methyl- 18-Crown-6) -3-Butyl-3H-imidazo Ru-1-ium tetrachloroaluminate, 1- (1-aza-methyl-15-crown-5) -3-methyl-3H-imidazol-1-ium chloride, 1- (1-aza-methyl-15 -Crown-5) -3-methyl-3H-imidazol-1-ium bromide, 1- (1-aza-methyl-15-crown-5) -3-methyl-3H-imidazol-1-ium iodide, 1- (1-Aza-methyl-15-crown-5) -3-methyl-3H-imidazol-1-ium hexafluorophosphate, 1- (1-aza-methyl-15-crown-5) -3-methyl -3H-imidazol-1-ium tetrafluoroborate, 1- (1-aza-methyl-15-crown-5) -3-methyl-3H-imidazol-1-ium trifluoromethanesulfonate, 1- ( 1-aza-methyl-15-crown-5) -3-methyl-3H-imidazol-1-ium tetrachloroaluminate and the like.

  The ionic liquid-supporting crown compound represented by the general formula [1] can be produced, for example, as follows. Here, a description will be given below by taking an example represented by the general formulas [52] and [77].

(In the formula, X ₂ represents a halogen atom, and A _{5 to} A ₈ , T ₁ , R ³⁸ , R ³⁹ and X ₁ are the same as above.)

In the general formulas [92] and [94], examples of the halogen atom represented by X ₂ include a fluorine atom, an iodine atom, a bromine atom, and an iodine atom.

That is, 1.2 mol of a halogenating agent (for example, triphenylphosphine and carbon tetrachloride, PCl ₃ , POCl ₃ , PCl ₅ or the like) is added to 1 mol of the hydroxy compound represented by the general formula [91]. In addition, the mixture is reacted by stirring at −20 to 140 ° C. for 0.5 to 24 hours to form a halogenated compound represented by the general formula [92], which is then used without a solvent or in a suitable solvent (for example, toluene, xylene, benzene). Aromatic hydrocarbons such as, for example, ethers such as tetrahydrofuran and dioxane), and 1.5 mol of the imidazole compound represented by the general formula [93] is added to the hydroxy compound, The mixture is reacted at 140 ° C. for 0.5 to 24 hours to obtain a halogen salt of the ionic liquid-supported crown compound according to the present invention represented by the general formula [94]. An ionic liquid-supported crown compound of the present invention having the desired counter anion (X ₁ ) can be obtained by reacting the desired HX ₁ with this to carry out an anion exchange reaction.

  In addition, a commercially available thing may be used for the hydroxy body shown by General formula [91], and what was synthesize | combined suitably according to the conventional method may be used.

(Wherein X ₂ represents a halogen atom, and A _{9 to} A ₁₁ , T ₁ , R ³⁸ , R ³⁹ and X ₁ are the same as above.)

In the general formulas [97] and [98], examples of the halogen atom represented by X ₂ include a fluorine atom, an iodine atom, a bromine atom, and an iodine atom.

That is, after 1.2 mol of NaH, KH, etc. was used in an appropriate solvent with respect to 1 mol of the amino compound represented by the general formula [95], the mixture was reacted at −20 to 140 ° C. for 0.5 to 24 hours to form a metal salt. Formaldehyde, hydroxyalkyl tosylate or the like is added, and the mixture is reacted with stirring at −20 to 140 ° C. for 0.5 to 24 hours to produce a hydroxy form represented by the general formula [96]. Next, 1.2 mol of a halogenating agent (for example, triphenylphosphine and carbon tetrachloride, PCl ₃ , POCl ₃ , PCl _5, etc.) is added to 1 mol of the hydroxy compound represented by the general formula [96]. Then, the mixture was reacted with stirring at −20 to 140 ° C. for 0.5 to 24 hours to produce a halide represented by the general formula [97]. This is dissolved in no solvent or in a suitable solvent (for example, aromatic hydrocarbons such as toluene, xylene, benzene, etc., ethers such as tetrahydrofuran, dioxane, etc.), and 1.5% of the resulting halogenated product is obtained. Mole of the imidazole compound represented by the general formula [93] is added and reacted with stirring at -20 to 140 ° C. for 0.5 to 24 hours. The halogen of the ionic liquid-supported crown compound according to the present invention represented by the general formula [98] Get salt. An ionic liquid-supported crown compound of the present invention having the desired counter anion (X ₁ ) can be obtained by reacting the desired HX ₁ with this to carry out an anion exchange reaction.

  In addition, as the amino compound represented by the general formula [95], a commercially available product may be used, or an amino compound appropriately synthesized according to a conventional method may be used.

  The ionic liquid-supported crown compound represented by the general formula [1] of the present invention can be used as a catalyst for various synthetic reactions using, for example, a crown ether such as 18-crown-6 as a phase transfer catalyst. It can be used as a catalyst for various synthetic reactions such as halogen substitution reaction, ether synthesis reaction, dehydrohalogenation reaction, benzyl sulfide formation reaction, ester synthesis reaction and the like, nucleophilic substitution reaction, olefin isomerization reaction, reduction reaction and the like.

  Further, when the ionic liquid-supported crown compound is used as a reaction catalyst (IL catalyst), 1 equivalent of the IL catalyst is dissolved in a reaction solvent, and for example, lithium salt, sodium salt, potassium salt, cesium salt are dissolved therein. A nucleophilic reagent consisting of a metal salt such as 1.5 equivalents and 0.2 equivalent of a reaction substrate can be added and reacted to produce the desired reaction product, for example, diethyl ether, ethyl acetate, toluene, etc. It is obtained by extracting with an organic solvent.

The reaction solvent to be used is not particularly limited as long as it is usually used as a reaction solvent, but an ionic liquid is preferable for the purpose of reuse. The ionic liquid is not particularly limited as long as it is usually used as an ionic liquid. For example, 1-ethyl-3-methylimidazolium methanesulfonate ([emim] [CH ₃ SO ₄ ]), 1- Ethyl-3-methylimidazolium trifluoromethanesulfonate ([emim] [CF ₃ SO ₄ ]), 1-ethyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imidate ([emim] [(CF ₃ SO ₄ ) ₂ N]), 1-ethyl-3-methylimidazolium tetrafluoroborate ([emim] [BF ₄ ]), 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim ] [PF ₆ ]), 1-butyl-3-methylimidazolium methanesulfonate ([bmim] [CH ₃ SO ₄ ]), 1-butyl-3-methylimidazolium trifluoromethanesulfonate ([bmim] _{[CF 3 SO 4]),} 1- butyl-3-methylimidazolium bis (trifluoromethyl Ruhoniru) imide salt _{([bmim] [(CF 3} SO 4) 2 N]), 1- butyl-3-methylimidazolium tetrafluoroborate _{([bmim] [BF 4]} ), 1- octyl -3 -Methylimidazolium hexafluorophosphate ([omim] [PF ₅ ]), 1-ethyl-3-methylimidazolium hexafluorophosphate ([emim] [PF ₆ ]) and the like.

  In addition, the reaction solvent containing the IL catalyst into which the metal ions after the completion of the reaction are taken is washed with water, whereby the metal ions taken into the IL catalyst can be easily removed. That is, since the activity of the IL catalyst is regenerated in this way, the same reaction can be repeated by reusing the reaction solvent containing the IL catalyst. This recycle process is shown below. 1- (Methyl-18-crown-6) -3-methyl-3H-imidazol-1-ium hexafluorophosphate is used as the ionic liquid-supported crown compound according to the present invention. Illustrative. }.

  The ionic liquid-supported crown compound of the present invention is difficult to recover and reuse in a reaction system despite the expensive catalyst that conventional crown ether compounds such as 18-crown-6 have. Without any problems, the ionic liquid-supported crown compound has a catalytic action like crown ether and can be efficiently recovered from the reaction system to regenerate and reuse the catalytic activity.

  Hereinafter, the present invention will be described in more detail with reference to Examples, Reference Examples, and Comparative Examples, but the present invention is not limited thereto.

Reference Example 1. Synthesis of 2- (chloromethyl) -18-crown-6 2- (hydroxymethyl) -18-crown-6 {603 mg, 2.00 mmol, manufactured by Tokyo Chemical Industry Co., Ltd. in 2 mL of carbon tetrachloride } Was added to the resulting solution, and 630 mg (2.4 mmol) of triphenylphosphine was added at room temperature under an argon atmosphere, followed by stirring and reaction at 60 ° C. for 2 hours. After completion of the reaction, the solvent was removed from the resulting reaction solution, and the resulting crude product was purified by silica gel column chromatography (chloroform / methanol = 9/1) to obtain 550 mg of the desired product as a colorless oil. (Yield: 88%).

Example 1. Synthesis of 1- (methyl-18-crown-6) -3-methyl-3H-imidazol-1-ium chloride

2- (Chloromethyl) -18-crown-6 (940 mg, 3.00 mmol) obtained in Reference Example 1 was dissolved in 3 mL of toluene, and 369 mg (4.5 mmol) of N-methylimidazole was added to the resulting solution at room temperature. The mixture was added and stirred at 110 ° C. for 24 hours. After completion of the reaction, the obtained product was extracted with 20 mL of water, and the obtained aqueous layer was concentrated under reduced pressure to obtain 1161 mg of the desired product as a yellow oil (yield: 98%).
Physical property data:
¹ HNMR (CD ₃ C (O) CD ₃ ) δ ppm: 4.43 (m, 23H), 4.96 (m, 3H), 5.44 (dd, J = 7, 13Hz, 1H), 5.65 (dd, J = 3, 13Hz , 1H), 8.89 (s, 2H), 10.99 (s, 1H).
¹³ C NMR (CD ₃ C (O) CD ₃ ) δ ppm: 36.73, 50.93, 70.13, 70.58, 70.99 (2C), 71.05 (2C), 71.26, 71.45 (2C), 71.53 (2C), 77.67, 123.96, 124.28, 139.13.

Example 2. Synthesis of 1- (methyl-18-crown-6) -3-methyl-3H-imidazol-1-ium hexafluorophosphate (IL catalyst)

1- (Methyl-18-crown-6) -3-methyl-3H-imidazol-1-ium chloride (395 mg, 1.00 mmol) obtained in Example 1 was dissolved in 3 mL of water, and the resulting solution was obtained. To the mixture, 0.5 mL of a 60% hexafluorophosphoric acid aqueous solution was slowly added at room temperature, followed by stirring for 5 hours. After completion of the reaction, the obtained reaction solution was extracted with 15 mL of methylene chloride, and then the obtained organic layer was washed with water until neutrality to obtain 280 mg of the desired product as a yellow oil (yield: 71% ).
Physical property data:
¹ H NMR (CD ₃ C (O) CD ₃ ) δ ppm: 3.67 (m, 23H), 4.00 (m, 3H), 4.46 (dd, J = 7, 15Hz, 1H), 4.64 (dd, J = 3, 15Hz , 1H), 7.65 (t, J = 1Hz, 1H), 7.66 (t, J = 1Hz, 1H), 8.95 (s, 1H).
¹³ C NMR (CD ₃ C (O) CD ₃ ) δ ppm: 36.45, 51.28, 69.65, 69.75, 70.63, 70.65, 70.70 (2C), 70.76 (2C), 71.08, 71.24, 71.47, 76.91, 123.54, 124.39, 138.06.
¹⁹ FNMR (CD ₃ C (O) CD ₃ ) δ ppm: 92.16 (d, J = 705 Hz).

Comparative Example 1 Acylation reaction of benzyl chloride (without catalyst)
1-butyl-3-methylimidazolium hexafluorophosphate ([bmim] [PF ₆ ]) (this [bmim] [PF ₆ ] was previously dried under reduced pressure at 80 ° C. for 5 hours) 5 mL 85.5 mg (0.5 mmol) of benzyl chloride was dissolved therein, and 73.5 mg (0.75 mmol) of potassium acetate was added to the resulting solution at room temperature, followed by stirring for 4 hours. After completion of the reaction, the target product was extracted with 20 mL of ether. Using the remaining [bmim] [PF ₆ ] solution, the same reaction was repeated four times. The results are shown in Table 1.

Comparative Example 2 Acylation of benzyl chloride (catalyst: 18-crown-6)
The target product was obtained in the same manner as in Comparative Example 1 except that a solution in which 26.4 mg (0.1 mmol) of 18-crown-6 was dissolved in [bmim] [PF ₆ ] was used. Using the remaining solution, the same reaction was repeated four times. The results are also shown in Table 1.

Example 3 Acylation reaction of benzyl bromide (catalyst: compound of Example 2)
[bmim] [PF ₆ ] solution (this [bmim] [PF ₆ ] was previously dried under reduced pressure at 80 ° C. for 5 hours.) 1- (methyl-) obtained in Example 2 in 5 mL 18-crown-6) -3-methyl-3H-imidazol-1-ium hexafluorophosphate (IL catalyst) (50.0 mg, 0.1 mmol, 0.2 equivalent) was dissolved, and the resulting solution (IL catalyst- [ bmim] [PF ₆ ] solution) were added 85.5 mg (0.5 mmol) of benzyl bromide and 73.5 mg (0.75 mmol, 1.5 equivalents) of potassium acetate at room temperature and allowed to react for 1 hour with stirring. After completion of the reaction, the target product was extracted with 20 mL of ether. The remaining solution was added to 10 mL of dichloroethane, and further 1 mL of water was added, and then the mixture was stirred at room temperature for 1 hour to remove potassium ions incorporated into the IL catalyst- [bmim] [PF ₆ ] solution. The remaining solution was dried under reduced pressure at 80 ° C. for 12 hours to remove dichloroethane and water. Using the remaining IL catalyst- [bmim] [PF ₆ ] solution, the same reaction was repeated four times. The results are also shown in Table 1.

  As is apparent from the results in Table 1, the acylation reaction was carried out without using a catalyst (Comparative Example 1) or the acylation reaction was carried out using 18-crown-6 as a catalyst (Comparative Example 2). Rather than using the IL catalyst according to the present application as a catalyst (Example 3), it was found that the yield was higher even when used several times.

Examples 4-7. Acylation of various bromides
A solution in which various bromides (0.5 mmol), various carboxylic acid potassium salts (0.75 mmol) and IL catalyst (0.1 or 0.2 equivalent) are dissolved in [bmim] [PF ₆ ] (5 mL) (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) After stirring at room temperature, the resulting product was extracted with 20 mL of diethyl ether. Next, the solvent was removed to obtain various acylated products. The results are shown in Table 2.

* Ac group = acetyl group, Ph = phenyl group As is clear from the results in Table 2, various bromides can be acylated using an IL catalyst as a catalyst. I understood.

Example 8 FIG. Fluorination of benzyl bromide (catalyst: IL catalyst)
[bmim] [PF _6] in solution 5 mL, was dissolved in IL catalyst obtained in Example 2, the resulting solution (IL catalyst - [bmim] [PF _6] solution) benzyl bromide 85.5 mg (0.5 mmol) and 43.6 mg (0.75 mmol) of potassium fluoride were added, and the mixture was stirred at 80 ° C. for 10 hours. After completion of the reaction, 20 mL of diethyl ether was added to the resulting reaction solution to extract benzyl fluoride. The remaining solution was dissolved in 10 mL of dichloroethane, and further 1 mL of water was added. Then, this was stirred at room temperature for 1 hour to remove potassium ions taken into the IL catalyst- [bmim] [PF ₆ ] solution. Then, this solution was dried under reduced pressure at 80 ° C. for 12 hours to recover an IL catalyst- [bmim] [PF ₆ ] solution. Using this IL catalyst- [bmim] [PF ₆ ] solution, the same reaction was repeated four times. The results are shown in Table 3.

Comparative Example 3 Fluorination of benzyl bromide (catalyst: 18-crown-6)
Benzyl fluoride was obtained in the same manner as in Example 8, except that a solution in which 26.4 mg (0.1 mmol) of 18-crown-6 was dissolved in [bmim] [PF ₆ ] was used. The same reaction was repeated twice again using the remaining solution. The results are also shown in Table 3.

As is apparent from the results in Table 3, it is better to use the IL catalyst according to the present application (Example 8) than when the fluorination reaction was performed using 18-crown-6 as the catalyst (Comparative Example 3). The yield was found to be high even after several uses. In other words, when 18-crown-6 is used as a catalyst, the taken-in potassium ion cannot be removed, so that the yield decreases every time it is followed. On the other hand, when the ionic liquid-supported crown compound of the present invention is used, potassium ions taken in can be easily removed by washing with water, so that the target product is good even if used several times. Obtained in yield.

Claims (6)

Formula [I]

(In the formula, T ₁ represents a linear alkylene group having 1 to 4 carbon atoms, R ³⁸ represents an alkyl group having 1 to 6 carbon atoms or an aralkyl group having 7 to 11 carbon atoms , and R ³⁹ represents a hydrogen atom or represents an alkyl group having 1 to 6 carbon atoms, X ₁ ^- represents a counter anion, organic synthesis reaction catalyst n is represented by representing) an integer of 1 to 3.. The counter anion represented by X ₁ ⁻ is a halide ion , hexafluorophosphoric acid, HPF ₆ , tetrachloroaluminic acid (HA1Cl ₄ ), or a general formula [36]

(Wherein R ⁴² represents a haloalkyl group), an imidic acid represented by the general formula [37]

(Wherein R ⁴³ represents a haloalkyl group), a carbon acid represented by the general formula [38]

(Wherein R ⁴⁴ represents a fluorine atom, a phenyl group or a cyano group optionally having a haloalkyl group as a substituent), boric acid represented by the general formula [39]

(Wherein R ⁴⁵ represents an alkyl group, a haloalkyl group, or a phenyl group optionally having an alkyl group or a halogen atom as a substituent) or a general formula [40]

(Wherein, R ⁴⁶ is an alkyl group,. Representing a haloalkyl group, or a substituent as an alkyl group or a phenyl group which may have a halogen atom) is derived from a carboxylic acid represented by claim 1 The catalyst for organic synthesis reaction as described in 2. In general formula [I] , T ₁ is a methylene group, R ³⁸ is a methyl group, R ³⁹ is a hydrogen atom, and X ₁ ⁻ is an anion derived from hexafluorophosphate (PF ₆ ⁻ ). The catalyst for organic synthesis reaction according to claim 1 . The catalyst for organic synthesis reaction according to claim 1, wherein n in the general formula [I] is 3. The catalyst for organic synthesis reaction represented by the general formula [I] is represented by the formula [99].

The catalyst for organic synthesis reaction of Claim 1 which is shown by these. The catalyst for organic synthesis reaction according to claim 1 , wherein the catalyst according to claim 1 is for nucleophilic substitution reaction.