WO2005113547A1

WO2005113547A1 - Ionic-liquid-supporting crown compound

Info

Publication number: WO2005113547A1
Application number: PCT/JP2005/009365
Authority: WO
Inventors: Atsunori Sano; Keiji Oono
Original assignee: Wako Pure Chemical Industries, Ltd.
Priority date: 2004-05-24
Filing date: 2005-05-23
Publication date: 2005-12-01
Also published as: JP4924034B2; JPWO2005113547A1

Abstract

A novel ionic-liquid-supporting crown compound which is usable as a catalyst capable of being recovered and reused. It is an ionic-liquid-supporting crown compound represented by the general formula [1] (wherein R1 is a group derived from a crown compound; R2 is a group derived from an ionic liquid; and T1 is a C1-8 alkylene chain).

Description

Crown compound supported on ionic liquid

Technical field

[0001] The present invention relates to a novel ionic liquid-carrying crown compound that enables recovery and reuse.

Background art

[0002] Ionic liquids are also referred to as room temperature molten salts, and have properties such as heat resistance, a wide liquid temperature range, non-volatility with almost no vapor pressure, low viscosity, and high ionic conductivity. Have.

[0003] Ionic liquids having such properties are expected to be applied to a wide range of fields, for example, as environmentally friendly reaction solvents for green chemistry, electrolyte solutions in the field of electrochemical devices, and the like. Is expected.

[0004] On the other hand, organic solvents that are commonly used as reaction solvents for various synthesis reactions are volatile, and their gases are harmful to the human body, and cause pollution and fire. Furthermore, these organic solvents have a problem that they are difficult to reuse after the reaction and are discarded, thereby causing environmental pollution.

[0005] In order to overcome these problems, attempts have been made to use ionic liquids as environmentally friendly reaction solvents. Since ionic liquids are non-volatile with almost no vapor pressure, they are easy to handle because they are not flammable or flammable, and they have the property of being hardly soluble in water or low-polarity organic solvents. Utilizing this property, if various reactions are carried out using an ionic liquid as a reaction solvent, the ionic liquid is extracted from the reaction system by, for example, extracting products and by-products with water or an organic solvent. Collection and reuse becomes possible.

[0006] On the other hand, crown ethers such as 18-crown-6 are widely used as phase transfer catalysts in various reactions such as nucleophilic substitution reactions. These crown ethers are expensive catalysts. Further, even if it is used as a reaction catalyst, it is difficult to recover it, so that there is a problem that it is costly to carry out the reaction using these crown ethers as a catalyst. [0007] Under such circumstances, it has been desired to develop a new catalyst which has a catalytic action of crown ether and can be recovered and reused after performing various reactions.

Disclosure of the invention

Problems to be solved by the invention

[0008] The present invention relates to a novel ionic liquid-supported crowned conjugate that can be used as a recoverable and reusable catalyst.

Means for solving the problem

[0009] The present invention has been made for the purpose of solving the above problems, and has a general formula [1]

[0010] R ¹ — τ -R ² [1]

(In the formula, R ¹ is a group derived from a crowny conjugate, R ² is a group derived from an ionic liquid, and T is an alkylene chain having 1 to 8 carbon atoms.) It is an invention of a crowned dagger and a catalyst comprising the same.

[0012] That is, as a result of the inventors' earnest studies to achieve the above object, the ionic liquid-carrying crowny conjugate of the present invention contains an ionic liquid and a crown compound in the molecule. Therefore, the present invention has been found to have a catalytic activity such as a crown ether such as 18-crown-6 and to facilitate the recovery from the reaction system, regeneration of the catalytic activity, and further reuse. Was completed.

The invention's effect

[0013] When the ionic liquid-carrying crown compound of the present invention is used as a catalyst, for example, a crown conjugate such as 18-crown-6 is recovered from a reaction system despite an expensive catalyst and is reused. Since it has an ionic liquid and a crown compound in a molecule that does not have the problem of being difficult to perform, it has a catalytic action like crown ether, can be efficiently recovered like an ionic liquid, and Since the recovered catalyst can easily regenerate its catalytic activity, it can be reused repeatedly.

BEST MODE FOR CARRYING OUT THE INVENTION

In the general formula [1], the group derived from the crown conjugate represented by R ¹ is, for example, a group derived from a macrocyclic polyether containing a hetero atom such as an oxygen atom, a sulfur atom, and a nitrogen atom. In Examples include groups derived from crown compounds having a 12-crown-4 skeleton, a 15-crown-5 skeleton, an 18-crown-6 skeleton, a 21-crown-7 skeleton, and a 24-crown-8 skeleton. Has the general formula [2]

[0016] {wherein, R ^{3 to} R ⁸ , m R ^{9 s,} and m R ^1G are each independently a bond bonded to T in the general formula [1], a hydrogen atom, an alkyl group , The general formula [3]

[0017] — CH ₂ R ^U [3]

(In the formula, R ¹¹ represents a hydroxy group, an alkoxy group, an aralkyloxy group or an acyloxy group.) A group represented by the general formula [4]

[0019] — CHR ¹² CH ₂ R ¹³ [4]

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

[0021] — C— R ¹⁴ [5]

O

[Wherein, R ¹⁴ represents a hydrogen atom, a hydroxy group, an alkyl group, an alkoxy group, an aryl group or an aryloxy group which may have an alkyl group as a substituent, or a general formula [6]

[0023] R ¹⁵

— N '[6]

, _R 16

(Wherein, R ¹⁵ and R ¹⁶ each independently represent an alkyl group.) A to A and m A are each independently an oxygen atom, a sulfur atom or

1 3 4

Is the general formula [7] [0025] \

N—R ¹⁷ [Sword

/

(Wherein, in the formula, R ¹⁷ has a bond bonded to the general formula [1], a hydrogen atom, an alkyl group, an alkylsulfur group, or an alkyl group as a substituent. Represents a aryl group, a benzenesulfol group, or a heterocyclic group). However, any of R ^{3 to} R ⁸ , m R ⁹ , m R ^1G , and A to A and m A are represented by the general formula [7].

1 3 4

Only one of the groups is a bond that bonds to T in the general formula [1]. M represents an integer of 1 to 5, and R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁷ and R ⁸ , and R ⁹ are each independently a cyclohexane ring together with carbons adjacent to each other. , A benzene ring or a naphthalene ring may be formed. The cyclohexane ring, benzene ring and naphthalene ring each independently represent an alkyl group, an alkenyl group, an acyl group, an acyloxy group, an alkoxycarbyl group, a morpholmethyl group or a decahydronaphthyl group. It may have a group. }.

In the above, “where R ^{3 to} R ⁸ , m R ⁹ , m R ^1C> , and A to A and m A

Of the cases where any one of 1 34 is a group represented by the general formula [7], only one is a bond that bonds to T in the general formula [1]. That is, in general formula [1], there is only one bond to be bonded to T in general formula [2], and the bond is derived from a crown compound represented by general formula [2]. Among the groups, when present in R ^{3 to} R ⁸ , m R ^{9 s} and m R ^1G , or R ^{17 represented} by the general formula [7], and the group containing R ¹⁷ is A to A And one of m A

1 3 4

This is the case. Specific groups derived from crowny daggers include, for example, general formulas

[8]

[Wherein, R to R, n R and n R are each independently a hydrogen atom, an alkyl group , The general formula [3]

[0030] — CH ₂ R ^U [3]

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

[0032] — CHR ¹² CH ₂ R ¹³ [4]

(Wherein, R ¹² and R ¹³ each independently represent a hydrogen atom, a hydroxy group, an alkoxy group, or an acyloxy group, provided that R ¹² and R ¹³ are not both hydrogen atoms ) Or a general formula [5]

[0034] — C— R ¹⁴ [5]

O

[Wherein, R ¹⁴ represents a hydrogen atom, a hydroxy group, an alkyl group, an alkoxy group, an aryl group or an aryloxy group which may have an alkyl group as a substituent, or a general formula [6] ] R ¹⁵

[6]

1 ⁶

(Wherein, R ¹⁵ and R ¹⁶ each independently represent an alkyl group.) A to A and n A are each independently an oxygen atom, a sulfur atom or

5 7 8

General formula [9]

[0038] \

N—R ²⁵ [9]

/

(Wherein, R ²⁵ represents a hydrogen atom, an alkyl group, an alkylsulfol group, an aryl group or a benzenesulfol group which may have an alkyl group as a substituent, or a heterocyclic group) .), And n represents an integer of 1 to 5. Also, R ¹⁸ and R ^19, R ²¹ and R ^22, and R 2 ³ and R ²⁴ are each independently together with the carbon adjacent to each other, hexane ring, may form a benzene ring or a naphthalene ring cyclohexylene . The cyclohexane ring, benzene ring and naphthalene ring each independently represent an alkyl group, an alkenyl group, an acyl group, an acyloxy group, an alkoxycarbyl group, a morpholmethyl group or a decahydronaphthyl group. It may have a group. } Or a general formula [10]

[Wherein, R ^{b to} R ^dl , p and p R ^dd each independently represent a hydrogen atom, an alkyl group

, The general formula [3]

[0042] — CH ₂ R ^U [3]

[0044] CHR ¹² CH ₂ R ¹³ [4]

[0046] One C—R ¹⁴ [5]

0

[0048] R ¹⁵

— N '[6]

(Wherein, R ¹⁵ and R ¹⁶ each independently represent an alkyl group.) A, A and p of A are each independently an oxygen atom, a sulfur atom or

9 10 11

Is the general formula [9]

[0050] \

N—R ²⁵ [9]

/

(In the formula, R ²⁵ represents a hydrogen atom, an alkyl group, an alkylsulfol group, an aryl group or a benzenesulfol group which may have an alkyl group as a substituent, or a heterocyclic group. You. ), And p represents an integer of 1 to 5. R ²⁶ and R ²⁷ , R ²⁸ and R ²⁹ , R ^3G 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. It may be. The cyclohexane ring, benzene ring and naphthalene ring each independently represent an alkyl group, an alkenyl group, an acyl group, an acyloxy group, an alkoxycarbyl group, a morpholmethyl group or a decahydronaphthyl. It may have a group. }.

The group derived from the ionic liquid represented by R ² includes a group represented by the general formula [11]

[0053] _{r34 qXi} O

( ^Wherein , R ^{34q +} represents a q-valent quaternary ammonium ion or a quaternary phospho-pium ion, q X— represents a counter-one, and q represents 1 or 2. )).

In the general formula [1], the alkylene chain having 1 to 8 carbon atoms represented by T generally has 1 carbon atom.

To 8, preferably 1 to 4, linear alkyl groups. Specific examples include methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, and otatamethylene. And a methylene group and an ethylene group.

An alkyl group represented by R ^{3 to} R ^{1C> 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] Examples thereof include those having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms, which may be linear, branched or cyclic, and specifically, for example, a methyl group, an ethyl group, n -Propyl, isopropyl, n-butyl, isobutyl, sec-butynole, tert-butynole, n-pentynole, isopentynole, sec-pentynole, tert-pentyl, neopentyl, n-hexyl Group, isohexyl group, sec-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 ^{n to} R ″ may be any of linear, branched or cyclic, usually having 1 to 6 carbon atoms. Preferred are those having 1-3, specifically, for example, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group , N-pentyloxy group , Isopentyloxy, sec-pentyloxy, tert-pentyloxy, neopentyloxy, n-hexyloxy, isohexyloxy, sec-hexyloxy, tert-hexyloxy, neohexyloxy, cyclo Examples include a propoxy group, a cyclobutoxy group, a cyclopentyloxy group, and a cyclohexyloxy group.

[0058] In the general formula [3], the Ararukiruokishi group represented by R ^11, includes generally one carbon number 7-11, specifically, for example, base Njiruokishi group, Fuenechiruokishi group, naphthylmethoxy And the like.

[0059] In the general formulas [3] and [4], examples of the acyloxy group represented by R ^{n to} R ¹³ include those derived from a carboxylic acid having usually 2 to 20 carbon atoms. For example, an acetyloxy group, a propionyloxy group, a butyryloxy group, an isoptyryloxy group, a valeryloxy group, an isovaleryloxy group, a pivaloyloxy group, a hexanoyloxy group, a heptanoyloxy group, an otatanyloxy group, a nonanoyloxy group, Decanoyloxy, dodecanoyloxy, tridecanoyloxy, tetradecanoyloxy, pentadecanoyloxy, hexadecanyloxy, heptadecanoyloxy, octadecanoyloxy, nonadecanyloxy Groups, icosanoyloxy group, benzoyloxy group, naphthoyloxy group and the like.

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] includes a linear, branched or cyclic alkyl group. Any one of which usually has 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 Group, _sec -butyl group, tert-butyl group, n-pentynole group, isopentynole group, sec-pentynole group, tert-pentynole group, neopentynole 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.

[0061] Having an alkyl group as a substituent represented by R ¹⁴ in the general formula [5], R ¹⁷ in the general formula [7], and R ²⁵ in the general formula [9], Furthermore, examples of the aryl group of the aryl group include those having 6 to L0 carbon atoms, and specific examples include a phenyl group and a naphthyl group. [0062] Examples of the alkyl group as the substituent include those having 1 to 3 carbon atoms, and specific examples include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. Can be

[0063] 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 tamenyl group.

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

[0065] Examples of the alkyl group as the substituent include those having 1 to 3 carbon atoms, and specific examples include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. Can be

Preferred specific examples of the aryloxy group having an alkyl group as a substituent include, for example, 2-methylphenoxy, 3-methylphenoxy, 4-methylphenoxy, 2,4-dimethylphenyl, and 3,5-dimethylphenyl. Examples thereof include an enoxy group and the like, and among them, for example, a 4-methylphenoxy group, a 2,4-dimethylphenoxy group and the like are preferable.

As the alkylsulfol 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 an alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group include R ^{3 to} R ^1G in the general formula [2], R ^{18 to} R ^{24 in the} general formula [8], and R ^{18 to} R ^{24 in the} general formula [8]. Examples are the same as the examples of the alkyl group represented by R ^{26 to} R ³³ in the formula [10].

[0068] have the general formula [7] in R ¹⁷ and the formula [9] as a substituent represented by at R ²⁵ an alkyl group, even I, benzenesulfonyl - The group, Examples of the benzenesulfonyl group include those in which 1 to 5, preferably 1 to 2 hydrogen atoms of an aromatic ring have been replaced by an alkyl group having 1 to 6 carbon atoms. Examples of the alkyl groups represented by ~ ¹ ° 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.

Preferred is a benzenesulfol group having an alkyl group as a substituent! / Specific examples thereof include a toluenesulfol group, a xylenesulfol group, and a cumenesulfol group. Can be

[0070] The heterocyclic group represented by the general formula [7] in R ¹⁷ and the formula [9] in in R ^25, one example nitrogen atom, a sulfur atom, a heteroatom of such as an oxygen atom As described above, those having preferably 1 to 3 are mentioned, and may be monocyclic or polycyclic.Specific examples include chenyl group, quinolyl group, isoquinolyl group, pyridyl group, thiazolyl group, furfuryl group, imidazolyl group and the like. No.

[0071] m in the general formula [2], n in the general formula [8] and p in the general formula [10] are usually integers of 1 to 5, preferably 1 to 3, more preferably 3

[0072] R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁷ and R ^{8 and} m R ⁹ and R ^{1C in} the general formula [2], and R ¹⁸ and R ^{18 in the} general formula [8] R ¹⁹ , R ²¹ and R ²² , n R ²³ and R ²⁴ , R ²⁶ and R ²⁷ , R ²⁸ and R ²⁹ , R ^3G and R ³¹ , and p R ^{32 in the} general formula [10] And R ³³ together with carbons adjacent to each other form a cyclohexane ring, a benzene ring and a naphthalene ring!

[0073] 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 and an alkoxycarbonyl group. Morphonylmethyl group, decahydronaphthyl group and the like.

[0074] Examples of the alkyl group mentioned as the substituent include those having a carbon number of usually 1 to 6, preferably 1 to 3, which may be linear, branched or cyclic. For example, R ^{3 to} R ^{1C> in} the above general formula [2], R ^{18 to} R ^{24 in} the above general formula [8], and R ^{26 to} R ³³ in the above general formula [10] And the same as those exemplified for the alkyl group.

Examples of the alkenyl group as the substituent include those having 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms, which may be linear, branched or cyclic. Is, for example, vinyl, aryl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methylaryl, 2-methylaryl, 1-methyl -Topoyl, 2-methyl-1-propyl, 1-pentyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl 1-butenyl group, 2-methyl-1-butyl group, 3-methyl-1-butyl group, 1,1-dimethyl-1-propyl group, 1-hexyl group, 2-hexyl -Le group, 3-hexyl group, 4-hexyl group, 5-hexyl group, 3-methyl-3-pentyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, And a cyclohexyl group.

[0076] Examples of the acyl group as the substituent include those derived from a carboxylic acid having usually 2 to 20 carbon atoms. Specific examples include an acetyl group, a propioyl group, a butyryl group, an isobutyryl group, Valeryl group, isovaleryl group, bivaloyl group, hexanoyl group, heptanyl group, otatanyl group, nonanoyl group, decanoyl group, dodecanoyl group, tridecanoyl group, tetradecanol group, pentadecanol group, hexanodecanol group, hexdecanoyl group, hexdecanoyl group Icosanoyl group, benzoyl group, naphthoyl group and the like.

[0077] Examples of the acyloxy group as the substituent include those derived from a carboxylic acid having 2 to 20 carbon atoms. Specifically, for example, R ^{n in the} above general formulas [3] and [4] ~ are the same as those of the exemplary Ashiruokishi groups represented by R ^13.

[0078] Examples of the alkoxycarboyl group 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 is represented by the general formula [2] ] in R ³ to R ^{1C to>,} similar to the example of the alkyl group represented by in R ¹⁸ to R ²⁴ and the one general formula [10] to at R ²⁶ to R ³³ in the general formula [8] Of those

[0079] In the general formula [8], R ¹⁸ to R ^22, n pieces of R ²³ and n number of R ²⁴ is is preferred that all hydrogen atoms.

A to A and n A's are preferably all oxygen atoms.

5 7 8

[0081] In the general formula [10], R ^{26 to} R ³¹ , p R ^32, and p R ³³ are preferably all hydrogen atoms.

[0082] A, A, and p A's are preferably all oxygen atoms.

9 10 11

[0083] In the general formula [1], macrocyclic Specific examples of groups derived from Kurauni匕合product represented by R ^1, containing heteroatoms example if an oxygen atom, a sulfur atom, to the as nitrogen atom Although it is not particularly limited as long as it is derived from a crown ether compound such as polyether, for example, “Synthetic Multidentate Macrocyclic Compounds—” RMIzattZj. Co-edited by J. Christensen, Toshiyuki Shono, translated by Shozo Yanagida, Keiichi Kimura) Table 2 • 1 in Chapter 2, “Synthesis of Crown Compounds” (see pages 63 to 107). And the like.

Preferred specific examples of the group derived from the crowny conjugate represented by the general formula [8] include, for example, the general formula [12]

(Wherein A to A are as defined above), a group derived from a 12-crown-4 skeleton represented by the following general formula:

(Wherein A to A and two A's are the same as those described above) derived from the 15-crown-5 skeleton

5 7 8

Group, general formula [14]

(Wherein, A to A and three A's are the same as described above)

5 7 8

Group, general formula [15]

(Wherein A to A and four A's are the same as described above), a group derived from a 21-crown-7 skeleton represented by the general formula [16]

[0094] (wherein, the A~A and 5 A the same.) Represented by the 24-crown - 8 group derived backbone, and among them, the formula _[17]

[0095] O one

0 〇 [17]

-o,

[0096] a group represented by the general formula [12], wherein A to A are oxygen atoms:

5 8

18]

A group represented by the following formula (corresponding to the general formula [13], wherein A to A and two A's are oxygen atoms);

A group represented by the formula [20] (corresponding to a group in which A to A and three A's are oxygen atoms in the general formula [14]);

[0102] (In the general formula [14], this corresponds to a case where A and one A are nitrogen atoms, and A, A and two A are oxygen atoms.)

[0104] (In the general formula [14], A and one A are a nitrogen atom, and correspond to A, A and two A ifi oxygen atoms.), A formula [22]

(In the general formula [14], A and one A are nitrogen atoms, and A, A and two A Corresponds to what is an oxygen atom. In particular, the group represented by the formula [19] is more preferable.

[0107] Preferable specific examples of the group derived from the crowny conjugate represented by the general formula [10] include, for example, general formula [23]

[0108]

Equation [24]

(Wherein A, A and two A's are the same as described above.)

9 10 11

Group of origin, general formula [25]

(In the formula, A, A and the three A's are the same as described above.)

9 10 11

Group of origin, general formula [26]

[0113]

(Wherein, A, A and the four A's are the same as described above.)

9 10 11

Group of origin, general formula [27]

(Wherein A, A and the five A's are the same as described above).

9 10 11

And the like. Among them, among others, the formula [28]

[0117] / ~ ₀ '

0 N- [28]

[0118] A group represented by the general formula [23], wherein A to A are oxygen atoms:

9 11

29]

[0120] a group represented by the general formula [24], wherein A, A and two A are oxygen atoms

9 10 11

Equivalent to ), Expression [30]

[0122] a group represented by the general formula [25], wherein A, A and three A are oxygen atoms

9 10 11 Equivalent to ) Is preferred, and a group represented by the formula [30] is more preferred.

[0123] In the general formula [11], the q-valent quaternary ^{ammonium ion represented} by R ^{34q +} includes, for example, the general formula [31]

[0124] _R 35

— NR ³⁷ [31]

R ³⁶

(In the formula, R ^{35 to} R ³⁷ each independently represent a hydrogen atom, an alkyl group, an aralkyl group, or an alkenyl group, provided that R ^{35 to} R ³⁷ are not hydrogen atoms. ), A general formula [32]

[0127] (wherein represents an alkyl group or an aralkyl group, and R represents a hydrogen atom or an alkyl group), and a general formula [33]

[0128]

(Wherein, k R ⁴ ″ s each independently represent an alkyl group, and k represents an integer of 1 to 5), such as a group represented by the following formula: , For example, the general formula [34]

[0131] (wherein, R ⁴¹ represents. An alkyl group) divalent quaternary Anmoniumuio emissions such as the group represented by.

[0132] q-valent quaternary phospho represented by R ^{34q +} - The Umuion, for example the general formula ^[35] [0133] R 35

— P— R ³⁷ [35]

R ³⁶

(In the formula, R ^{35 to} R ³⁷ are the same as described above.) A monovalent quaternary phospho-pium ion such as a group represented by the following formula: Etc.

[0135] General formula [31] - In [35], the alkyl group represented by R ³⁵ to R ^41, a linear, Yogu usually 1 to 6 carbon atoms either branched or cyclic, Preferred are those having 1 to 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, isopentyl, sec-pentyl, tert-pentyl, neopentyl, n-hexyl, isohexyl, sec-hexyl, tert-hexyl, neohexyl, Examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

[0136] In the general formulas [31], [32] and [35], the aralkyl group represented by R ^{35 to} R ³⁸ is usually an aralkyl group having 7 or more carbon atoms: L 1. Are, for example, benzyl, phenyl, 1-phenyl, 2-phenylpropyl, 3-phenylpropyl, phenylphenyl, 1-methyl-3-phenylpropyl, naphthylmethyl And the like.

In the general formulas [31] and [35], the alkenyl group represented by R ^{35 to} R ³⁷ may be any of linear, branched or cyclic and usually has 2 to 20 carbon atoms. And specifically include, for example, a butyl group, an aryl group, a 1-propyl group, an isopropyl group, a 1-butyl group, a 2-butyl group, a 3-butyl group, and a 1-methylaryl group. , 2-methylaryl, 1-methyl-1-propyl, 2-methyl-1-propyl, 1-pentyl, 2-pentenyl, 3-pentyl , 4-pentyl, 1-methyl-1-butyl, 2-methyl-1-butul, 3-methyl-1-butul, 1,1-dimethyl-1-probel, 1 -Hexyl group, 2-hexyl group, 3-hexyl group, 4-hexyl group, 5-hexyl group, 3-methyl-3-pentyl group, Heptenyl, otathenyl, noneryl, decenyl, decenyl, dodecenyl Group, tridecenyl group, tetradecenyl group, pentadecenyl group, hexadecenyl group, heptadecyl group, 9-octadecyl group, nonadecyl group, icosyl group, cyclopropanol group, cyclobutenyl group, cyclopentyl group And a cyclohexyl group.

[0138] In the general formula [33], k is an integer of usually 1 to 5, preferably 1 to 2.

[0139] In the general formula [11], as the counter-on represented by X—, a halogen atom, or hexafluorophosphoric acid, (HPF), tetrachloroaluminic acid (HA1C1), a general formula [36] [0140] (R ⁴² so ₂ ) ₂ NH [36]

[0141] (wherein, R ⁴² represents a haloalkyl group), a general formula [37]

^{_{[0142] (R 43 S0 2}} ) 3 CH [37]

[0143] A carbon acid represented by the formula (where R ⁴³ represents a haloalkyl group);

^{[0144] HB (R 44)} 4 [38]

[0145] In the formula, R ⁴⁴ represents a fluorine atom, a phenyl group or a cyano group which may have a haloalkyl group as a substituent, and a boric acid represented by the general formula [39]

[0146] R ⁴⁵ S0 ₃ H [39]

(Wherein, R ⁴⁵ represents an alkyl group, a haloalkyl group, or an alkyl group or a halogen atom as a substituent, and may also represent a phenyl group). General formula [40]

[0148] ⁴⁶ C00H [40]

(In the formula, R ⁴⁶ has an alkyl group, a haloalkyl group, or an alkyl group or a halogen atom as a substituent, and may be a phenyl group.) What you do.

[0150] Examples of the halogen atom exemplified as the counter-on represented by X include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0151] In the general formulas [36], [37], [39], and [40], the haloalkyl group represented by R ⁴² , R ⁴³ , R ^45, and R ⁴⁶ is a straight-chain or branched-chain haloalkyl group. Alternatively, part or all of the hydrogen atoms of the alkyl group having 1 to 20 carbon atoms, and preferably 1 to 10 carbon atoms, which may be any of cyclic ones, are halogen atoms (eg, fluorine, chlorine, bromine, iodine, etc.). Examples thereof include substituted ones. Specific examples include a fluoromethyl group, a chloromethyl group, a bromomethyl group, an odomethyl group, a difluoromethyl group, a trifluoromethyl group, a trichloromethyl group, a tribromomethyl group, a trimethylmethyl group, and a trifluoromethyl group. Loethyl group, trichloroethyl group, tribromoethyl group, triodoethyl group, pentafluoroethyl group, pentachloroethyl group, pentablomoethyl group, pentanoethyl group, Riffle O b propyl, heptafluoro full O b propyl group, hepta-chloropropyl group, hepta-bromopropyl group, hepta ® over de propyl, DOO Rifluorobutyl group, nonafluorobutyl group, nonachlorobutyl group, nonabromobutyl group, nonaodobutyl group, trifluoropentyl group, pendecafluoropentyl group, pendecachloropentyl group, pendecabromopentyl group, Pendecayodopentyl, trifluorohexyl, tridecafluorohexyl, tridecachlorohexyl, tridecabromohexyl, tridecaiodohexyl, trifluoheptyl, pentadecafluoroheptyl Pentadecachloroheptyl group, pentadecabromoheptyl group, pentadecayodoheptyl group, trifluorooctyl group, heptadecafluorooctyl group, heptadecachlorooctyl group, heptadecabromooctyl group, heptadecayo 1-octyl group, trifluoromethyl group, Decafluoronol group, nonadecanol group, nonadecabul monol group, nonadecanol group, trifluorodecyl group, perfluorodecyl group, perchlorodecyl group, perbromodecyl group, perododecyl group , Perfluoroundecyl group, perchloroundecyl group, mound decyl group at parb mouth, perdodecyl group, perfluorododecyl group, rhododecyl group at park mouth, mododecyl group at parb mouth, parodododecyl group, perfluorotridecyl Group, perchlorotridecyl group, perbromotridecyl group, perodotridecyl group, perfluorotetradecyl group, park mouth lotetradecyl group, perbromotetradecyl group, perodotetradecyl group, perflu O-pentadecyl group, perchloropentadecyl group, perbromopentadecyl group Group, period pentadecyl group, perfluorohexadecyl group, perchlorohexadecyl group, monobromohexadecyl group, periodohexadecyl group, perfluoroheptadecyl group, perchloroheptadecyl group, perbromoheptadecyl group, paro Heptadecyl group, perfluorooctadecyl group, perchlorooctadecyl group, perbromooctadecyl group, perodooctadecyl group, perfluorononadecyl group, perchlorononadecyl group , Perna mononadecyl, perodononadecyl, perfluoro leucosyl, norchloroicosinole, pericolate moikosinole, peridocosinole, perphnoleo cyclohexyl Group, perchlorocyclohexyl group, peroxycyclohexyl group, perdocyclohexyl group, etc. And the like.

In the general formula [38], which may have a haloalkyl group as the substituent represented by R ⁴⁴ Hue - The group, for example Hue - group, Hue - 1-5 group, preferably Is 1-3 In which a hydrogen atom is replaced by a haloalkyl group.

[0153] The haloalkyl group exemplified as these substituents may be a straight-chain, branched or cyclic, usually having 1 to 20, preferably 1 to 10 carbon atoms, part of a hydrogen atom of an alkyl group. Or those in which all are substituted with halogen atoms (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.), and specifically, for example, those represented by the above general formulas [36], [37], [39] And the same haloalkyl groups as R ⁴² , R ⁴³ , R ⁴⁵ and R ⁴⁶ in [40].

[0154] In the general formulas [39] and [40], the alkyl group represented by R ⁴⁵ and R ⁴⁶ may be any of linear, branched or cyclic, and usually has 1 to 20 carbon atoms. Preferred are 1 to: L0, and specifically, for example, R ^{3 to} R ^{1C> in} the above general formula [2], R ^{18 to} R ^{24 in} the above general formula [8] and the above The same as the examples of the alkyl group represented by R ^{26 to} R ³³ in the general formula [10], n-heptyl group, isoheptyl group, sec-heptyl group, tert-heptyl group, neoheptyl Group, n-octyl group, isooctyl group, sec-octyl group, tert-octyl group, neooctyl group, n-nor group, isonol group, sec-nor group, tert-nor group, Neononyl group, n-decyl group, isodecyl group, sec-decyl group, tert-decyl group, neodecyl group, n-pentadecyl group, isopendecyl group, sec-benzyldecyl group, tert-benzyl group , Neodondecyl, n-dodecyl, isododecyl, sec-dodecyl, tert-dodecyl, neododecyl, n-tridecyl, isotridecyl, sec-tridecyl, tert-tridecyl, neotridecyl, n -Tetradecyl, isotetradecyl, sec-tetradecyl, tert-tetradecyl, neotetradecyl, n-pentadecyl, isopentadecyl, sec-pentadecyl, tert-pentadecyl, neopentadecyl, n -Hexadecyl, isohexadecyl, sec-hexadecyl, tert-hexadecyl, neohexadecyl, n-heptadecyl, isoheptadecyl, sec-heptadecyl, tert-heptadecyl, neo Heptadecyl group, n-octadecyl group, isooctadecyl group, sec-octadecyl group, tert-octadecyl group, neo Cutadecyl, n-nonadecyl, isononadecyl, sec-nonadecyl, tert-nonadecyl, neononadecyl, n-icosyl, isoicosyl, sec-icosyl, tert-icosyl, neoicosyl, cyclopropyl , Cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl And the like.

[0155] In the general formulas [39] and [40], examples of the phenyl group which may have an alkyl group or a halogen atom as a substituent represented by R ⁴⁵ and R ⁴⁶ include phenyl. Examples thereof include those in which 1 to 5, preferably 1 to 3, hydrogen atoms of a group or a ball group are substituted with an alkyl group or a halogen atom.

[0156] Examples of the alkyl group mentioned as the substituent include those having a carbon number of usually from 1 to 20, preferably from 1 to L0, which may be any of linear, branched or cyclic. Examples thereof include those similar to the examples of the alkyl group represented by R ⁴⁵ and R ⁴⁶ in the general formulas [39] and [40].

[0157] Examples of the halogen atom mentioned as the substituent include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.

The group derived from the ionic liquid ^represented by R ^{34q + represented} by the general formula [11] includes, for example, a group derived from an imidazolium cation represented by the general formula [32], and a group represented by the general formula [33] Among these groups, groups derived from an imidazole cation represented by the general formula [32] are more preferable.

[0159] Preferable specific examples of the group derived from the quaternary ammonium cation represented by the general formula [31] include, for example, triethyl ammonium ion, tri-n-propyl ammonium ion, and tri-n-butyl ammonium ion. , Tri-n-pentylammonium-ammion, tri-n-hexylammonium-ammonium, tri-n-heptylammonium-ammonium, tri-n-octylammonium-ammonium, tri-n-nor-ammonium-ammonium, tri-n-ammonium n-decylammonium-ammonium, tri-n-pentadecylammonium-pam ion, trilauryl (dodecyl) ammonium ion, tri-n-tridecylammonium-pam ion, trimyristyl (tetradecyl) ammonium-pam ion, tri-n-pentantadecylammonium-pam ion, tri-ion Cetyl ammonium-pium ion, tri-n-heptadecylammo-pium ion, dioctadecy Methylammonium, didecylmethylammonium, dinomethylmethylammonium, dioctylethylammonium, diheptylpentylammonium, diheptylpropylammonium, diheptylpropylammonium, diheptylmethylammonium, ammonium ion Hexylbutylammonium-diamine, dihexylethylammonium-diamine, nor-pentylammonium-diamine ion, hexyldiamine Pentylammonium, dipentylbutylammonium-dimone, dipentylmethylammonium-dimmeion, octyldibutylammonium-dimmeion, hexyldibutylammonium-dimmeion, heptyldipropylammonium-dimmeion, hexyldipropylammonium-dimmeion, dipropylmethyl Ammonium, tetradecyl getyl ammonium, octyl getyl ammonium, octadecyl dimethyl ammonium, heptadecyl dimethyl ammonium, hexadecyl dimethyl ammonium, dodecyl dimethyl ammonium -Pemmion, decyldimethylammo -Pemmion, nordimethylammo -Pemmion, octyldimethylammo -Pemmion, hexyldimethylammonium -Pemmion, ethyldimethylammo- Demion, decylbutylpropylum-ammion, decylbutylethylammonium-ammion, undecylp-ammonium-pyriumammonium-ammion, nor-octylmethylammonium-ammion, noroctylmethylammonium-ammion, noelhexyl Butylammonium, norhexylmethylammonium, norpentylmethylammonium, octylhexylpentylammonium, octylhexylpentylammonium, octylhexylpropylammonium, Octylhexylmethylammonium ion, octylpentylbutylammonium ion, octylpentylpropylammonium ion, octylpentylmethylammonium ion, octylbutylmethylammonium ion Octylethyl methyl ammonium ion, heptylpentyl methyl ammonium ion, hexylpentyl butyl ammonium ion, hexylpentyl methyl ammonium ion, hexyl butyl methyl ammonium ion, ethyl butyl ammonium ion Groups derived from trialkylammonium cations, such as dioleyl (9-octadecyl) methylammonium cation; groups derived from dialkylalkylammonium cations, such as dioleyl (9-octadecyl) methylammonium ion; Groups derived from quaternary ammonium cations such as groups derived from aralkyldialkylammonium cations such as ammonium ion, benzyldipropylammonium and benzyldi-n-propylammonium ion.

Preferred specific examples of the group represented by the general formula [32] include, for example, 3-methylimidazolym Ion, 3-ethinoreimidazolium ion, 3-butinoreimidazolium ion, 3-pentinoreimidazolium ion, 3-hexinoreimidazolium ion, 3-otachinoreimidazolium ion, 3-decylimidazolidium ion, 3- Groups derived from alkyl-substituted imidazolium cations such as dodecyl imidazolium ion, 3-tetradecyl imidazolium ion, 3-hexadecyl imidazolium ion, and 3-octadecyl imidazolium ion; for example, 3-benzyl imidazolium ion; Groups derived from aralkyl-substituted imidazolym cations such as 3-phenylpropylimidazolym ion, such as 2,3-dimethylimidazolym ion, 2-methyl-3-ethylimidazolium ion, 2-methyl-3-butylimidazolym ion, 2 -Methyl-3-propylimidazoli Ion, and 2-methyl-3-hexyl imidazolium Riu-ion, a group derived from an alkyl 2-substituted imidazolium cation of 2 such Kisadeshiru imidazo Riu-ion to the methyl-3-

[0161] Preferable specific examples of the group represented by the general formula [33] include, for example, pyridium-ion, 3-methylpyridin-ion, 3-ethylpyridin-ion, 4-methylpyridin-ion, 4-ethylpyridin-ion, and 3 And groups derived from a pyridium-cation such as 1,4-dimethylpyridin-dumion and 3,5-dimethylpyridin-dumion.

[0162] Preferable specific examples of the group represented by the general formula [34] include, for example, N-methyl-4,4'-bipyridium-dumion, N-ethyl-4,4'-bipyridi-dumion, N-propyl -4,4'-bipyridi-dumion, N-butyl-4,4'-bipyridy-dumion, N-pentyl-4,4'-vipyridy-dumion, N-hexyl-4,4'-dibirid- Pemion, N-heptyl-4,4'-bividium-ion, N-octyl-4,4'-bividium-ion, N-nor-4,4'-Vividium-ion, N-decyl-4 4'-Viviridi-ammion, N-Pindecyl-4,4'-Vibilidi-aluminum, N-dodecyl-4,4'-Vibilidi-aluminum, N-tridecyl-4,4'-Viviridi-aluminum, N-tetradecyl- 4,4'-Bibidium-ion, N-pentadecyl-4,4'-Bibidium-ion, N-hexadecyl-4,4'-Viviridium-ion, N-Heptadecyl-4,4'-vivil N-alkyl- such as di-ion, N-otatadecyl-4,4'-biviridium-ion, N-nonadecyl-4,4'-biviridium-ion, N-ycosyl-4,4'-bivilidium-ion Groups derived from 4,4'-biviridium cation, e.g., N-benzyl-4,4'-biviridium-N-aralkyl-4,4'-biviridion -Pem cation-derived groups. [0163] Preferable specific examples of the group represented by the general formula [35] include, for example, trimethylphospho-pam ion, triethylphospho-pam ion, tripropylphospho-pam ion, tributylphospho-pam ion, tripentylphospho-pam ion, and tripentylphospho-pam ion. Hexylphospho-perm ion, triheptinolephospho-perm ion, trioctinolephospho-perm ion, trino-norrephospho-perm ion, tridecylphospho-perm ion, tridecylphospho-perm ion, tridodecyl phospho-perm ion, tri (tridecyl) phospho-perm ion, Tri (tetradecyl) phospho-pum ion, tri (hexadecyl) phospho-pum ion, tri (heptadecyl) phospho-pumion, tri (octadecyl) phospho-pum ion, tri (nonadecyl) phospho-pum ion, trico Groups derived from trialkylphosphonium cations such as silphospho-permion and dihexylmethylphospho-permion, for example, groups derived from dialkylalkylphospho-perm cations such as dioleyl (9-octadecyl) methylphospho-permion, such as benzyl Examples include groups derived from quaternary phospho-pum cations such as groups derived from aralkyl dialkyl phospho-pum cations such as dimethyl phospho-pum ion, benzyl getyl phospho-pum ion, and benzyl dipyrroyl phospho-pum ion.

[0164] Preferable specific examples of the imido acid represented by the general formula [36] include, for example, bis (trifluoromethylsulfol) imidic acid, bis (pentafluoroethylsulfol) imidic acid, and bis (heptafluroic acid). (Fluoropropylsulfol) imidic acid, bis (nonafluorobutylsulfol) imidic acid, bis (perfluoropentylsulfol) imidic acid, bis (perfluorohexylsulfuryl) imide Acid, bis (perfluorohexylsulfol) imidic acid, bis (perfluorooctylsulfol) imidic acid, bis (trichloromethylsulfol) imidic acid, bis (pentachloroethylsulfol) imidic acid , Bis (heptachloropropylsulfol) imidic acid, bis (nonachlorobutylsulfol) imidic acid, bis (perchloropentylsulfol) imide Acid, bis (perchlorohexylsulfonyl) imidic acid, bis (perchloroheptylsulfonyl) imidic acid, bis (perchlorooctylsulfonyl) imidic acid, bis (trimethylmethylsulfonyl) imidic acid, Bis (pentabole motylsulfol-l) imidic acid, bis (heptabromopropylsulfol-l) imidic acid, bis (nonab mouth mobutylsulfol-l) imidic acid, bis (nobromopentylsulfol-l) imidic acid, bis (perbromo Hexylsulfonyl) imid acid, bis (perbromoheptylsulfonyl) imidic acid, bis (perbromooctylsul) And (bis (trifluoromethylsulfol) imidic acid, bis (trifluoromethylsulfolyl) imidic acid, and bis (perfluorooctylsulfo) imidic acid. -I) imidic acid and the like are preferred.

[0165] Preferable specific examples of the carbon acid represented by the general formula [37] include, for example, tris (trifluoromethylsulfol) carbon acid, tris (pentafluoroethylsulfol) carbon acid, and tris (nonafluoro). Tris (perfluoropentylsulfol) carboxylic acid, tris (perfluoropentylsulfol) carbonic acid, tris (perfluoropentylsulfol) carbonic acid, tris (perfluoropentylsulfol) carbonic acid, Tris (perfluoroheptylsulfol) carbonic acid, Tris (perfluorooctylsulfol) carbonic acid, Tris (trichloromethylsulfol) carbonic acid, Tris (pentachloroethylsulfol) carbonic acid Acid, tris (non-chloro propylsulfol) carbonic acid, tris (perchlorobutylsulfol) carbonic acid, tris (perchloropentylsulfol) carbonic acid, tris Tris (perchlorohexylsulfonyl) carbonic acid, tris (perchlorooctylsulfonyl) carbonic acid, tris (trichloromethylsulfonyl) carbonic acid, C) tricarboxylic acid, tris (nonabromopropylsulfur) carbonic acid, tris (perbutyl molybylsulfur) carbonic acid, tris (perbromopentylsulfur) carbonic acid, tris (perbromohexylsulfur) carbon Acid, tris (perbromoheptylsulfol) carbonic acid, tris (perbromooctylsulfol) carbonic acid and the like. Among them, for example, tris (trifluoromethylsulfol) carbonic acid and tris (pentafluorophenol) Tylsulfonyl) carbonic acid, tris (perfluorooctylsulfonyl) carbonic acid and the like are preferred, .

[0166] Preferred 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 {bis (triphenylmethyl) phenyl} boric acid; and the like, among which tetrafluoroboric acid is preferable.

[0167] Preferable specific examples of the sulfonic acid represented by the general formula [39] include, for example, alkylsulfonic acids such as methanesulfonic acid, ethanesulfonic acid and propanesulfonic acid, for example, trifluoromethanesulfonic acid, pentafluoroethane and the like. Sulfonic acid, heptafluoropropanesulfonic acid, nonafluorobutanesulfonic acid, perfluoropentanesulfonic acid, perfume Hexane sulfonic acid, perfluoroheptanesulfonic acid, perfluorooctanesulfonic acid, trichloromethanesulfonic acid, pentachloroethanesulfonic acid, heptachloropropanesulfonic acid, nonachlorobutanesulfonic acid, perchloropentanesulfonic acid, / Hexanesulfonic acid, perchloroheptanesulfonic acid, octanesulfonic acid, tribromomethanesulfonic acid, pentabromoethanesulfonic acid, heptabromopropanepansulfonic acid, nonabromobutanesulfonic acid, perbromopentanesulfonic acid Acids, haloalkylsulfonic acids such as -bromohexansnolephonic acid, perbromoheptanesnoleonic acid, perbromooctanesulphonic acid, and arylsulphonic acids such as benzenesulfonic acid, for example p-toluenes Examples thereof include alkyl-substituted benzenesulfonic acids such as sulfonic acid (tosylic acid), and among them, for example, trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, nonafluoropropanesulfonic acid, and perfluorooctanesulfonic acid. Are preferred.

[0168] 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, for example, perfluoroacetic acid, perfluoropropionic acid, and perfluorobutane. Acid, perfluorooctanoic acid, chloroacetic acid, chloroacetic acid, perchloropropionic acid, perchlorobutanoic acid, chlorooctanoic acid, perbromoacetic acid, perbromopropionic acid, perbromobutanoic acid, perbromobutanoic acid And the like.

[0169] Examples of the ionic liquid-supported crown conjugate represented by the general formula [1] include those represented by the following general formulas [41] to [90].

: 47]

[52]

S9C600 / S00Zdf / X3dl ^ n / SOOZ OAV οε

S9C600 / S00Zdf / X3dl ^ n / SOOZ OAV

[0200] (where R ³⁵ ~! ^ T, A ~ A, 1 ~ 5 A, A, A, 1 ~ 5 A, X and k are

1 5 7 8 9 10 11 1 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] (particularly, A to A and A to A are oxygen

Those having 5 8 9 11 atoms are preferred. ) Are preferred, and those represented by the general formula [52] (especially those in which A to A are oxygen atoms are more preferred) are more preferred.

5 8

[0201] Preferable specific examples of the ionic liquid-carrying crown compound represented by the general formula [1] include, for example, 1- (methyl-18-crown-6) -3-methyl-3H-imidazole-1-dium chloride, 1- (Methyl-18-crown-6) -3-methyl-3H-imidazole-1-dim bromide, 1- (methyl-18-crown-6) -3-methyl-3H-imidazole-1-dimoxide , 1- (methyl-18-crown-6) -3-methyl-3H-imidazole-1-dimhexafluorophosphate, 1- (methyl-18-crown-6) -3-methyl-3H-imidazole 1-dimethyl tetrafluoroborate, 1- (methyl-18-crown-6) -3-methyl-3H-imidazole-1-dimethyl trifluoromethanesulfo Acid salt, 1- (methyl-18-crown-6) -3-methyl-3H-imidazole-1-dium tetraclomate Aluminate, 1- (methyl-18-crown-6) -3-butyl-3H -Imidazole-1-dium chloride, 1- (methyl-18-crown-6) -3-butyl-3H-Imidazole-1-dium bromide, 1- (methyl-18-crown-6) -3-butyl- 3H-imidazole-1-dimoxide, 1- (methyl-18-crown-6) -3-butyl-3H-imidazole-1-dimethylhexafluorophosphate, 1- (methyl-18-crown-6) -3 -Butyl-3H-imidazole-1-dium tetrafluoroborate, 1- (methyl-18-crown-6) -3-butyl-3H-imidazole-1-dium trifluoromethanesulfonate, 1- (Methyl-18-crown-6) -3-butyl-3H-imidazole-1-dimethyltetrachloroaluminate, 1- (methyl-15-crown-5) -3-methyl-3H-imida 1-dimethyl chloride, 1- (methyl-15-crown-5) -3-methyl-3H-imidazole-1-dim bromide, 1- (methyl-15-crown-5) -3-methyl- 3H-imidazole-1-dimension, 1- (methyl-15-crown-5) -3-methyl-3H-imidazole-1-dimethylhexafluorophosphate, 1- (methyl-15-crown-5)- 3-methyl-3H-imidazole-1-dium tetrafluoroborate, 1- (methyl-15-crown-5) -3-methyl-3H-imidazole-1-dium trifluoromethanesulfonate, 1- (Methyl-15-crown-5) -3-methyl-3H-imidazole-1-dium tetrachloroaluminate, 1- (1-aza-18-crown-6) -3-methyl-3H-imidazole- 1-dimethyl chloride, 1- (1-aza-methyl-18-crown-6) -3-methyl-3H-imidazole-1-dimethyl bromide, 1- (1-aza-methyl-18) -Crown-6) -3- Tyl -3H-imidazole-1-dimethoxy, 1- (1-aza-methyl-18-crown-6) -3-methyl-3H-imidazole-1-dimhexafluorophosphate, 1- (1-aza-methyl-18-crown-6) -3-methyl-3H-imidazole-1-dium tetrafluoroborate, 1- (1-aza-methyl-18-crown-6) ) -3-Methyl-3H-imidazole-1-dimethyl trifluoromethanesulfonate, 1- (1-aza-methyl-18-crown-6) -3-methyl-3H-imidazole-1-dimethyl tetraclo Oral aluminate, 1- (1-aza-methyl-18-crown-6) -3-butyl-3H-imidazole-1-dimethyl chloride, 1- (1-aza-methyl-18-crown-6) ) -3-Butyl-3H-imidazole-1-dimethyl bromide, 1- (1-aza-methyl-18-crown-6) -3-butyl-3H-imidazole-1-dimethyl bromide, 1- (1- Aza-methyl -18-crown-6) -3-butyl -3H-imidazole -1- Dimethylhexafluorophosphate, 1- (1-aza-methyl-18-crown-6) -3-butyl-3H-imidazole-1-yl Tetrafluoroborate, 1- (1-aza-methyl-18-crown-6) -3-butyl-3H-imidazole-1-dium trifluoromethanesulfonate, 1- (1- Aza-methyl -18-crown-6) -3-butyl-3H-imidazole-1-dium tetrachloroaluminate, 1- (1-aza-methyl-15-crown-5) -3-methyl -3H-imidazole-1-dimethyl chloride, 1- (1_aza-methyl -15-crown-5) -3-methyl -3H-imidazole-1-dimethyl bromide, 1- (1-aza-methyl -15-crown-5) -3-methyl-3H-imidazole-1-dimoxide, 1- (1-aza-methyl-15-crown-5) -3-methyl-3H-imidazole-1-dim Hexafluorophosphate, 1- (1-aza-methyl-15-crown-5) -3-methyl-3H-imidazole-1-dium tetrafluoroborate, 1- (1-aza-methyl-15) -Crown-5) -3-methyl-3H-imidazole-1-dim trif Fluoromethanesulfonate, 1- (1-aza-methyl-15-crown-5) -3-methyl-3H-imidazole-1-dimethyl tetrachloroaluminate and the like.

[0202] The ionic liquid-carrying crowned conjugate represented by the general formula [1] can be produced, for example, as follows. Here, C is explained as follows, taking as an example those represented by general formulas [52] and [77].

(In the formula, X represents a halogen atom, and A to A, T, R ³⁸ , R ³⁹ and X are the same as described above.)

2 5 8 1 1

[0205] In the general formulas [92] and [94], the halogen atom represented by X is, for example, fluorine.

2 Elemental atoms, iodine atoms, bromine atoms, iodine atoms and the like.

[0206] That is, 1 mol of the hydroxy compound represented by the general formula [91] is added to 1.2 mol of a halogenating agent (for example, triphenylphosphine and carbon tetrachloride, pel, POC1, PC1

3 3 5 etc. ), And the mixture is stirred and reacted at 20 to 140 ° C for 0.5 to 24 hours to produce a halogenated compound represented by the general formula [92]. Dissolved in aromatic hydrocarbons such as toluene, xylene, benzene, etc., for example, ethers such as tetrahydrofuran, dioxane, etc.), and 1.5 moles of the imidazole derivative represented by the general formula [93] with respect to the hydroxy compound. The product is added and the mixture is stirred and reacted at 20 to 140 ° C. for 0.5 to 24 hours to obtain a halogen salt of the ionic liquid-carrying crowny conjugate according to the present invention represented by the general formula [94]. The desired HX is reacted therewith to carry out an anion exchange reaction to obtain the ionic liquid-carrying crowned conjugate of the present invention having the desired counter-on (X).

[0207] As the hydroxy compound represented by the general formula [91], a commercially available hydroxy compound or a compound appropriately synthesized according to a conventional method may be used.

(In the formula, X represents a halogen atom, and A to A, T, R ^d R ^d9 and X are the same as described above.)

2 9 11 1 1

[0210] In the general formulas [97] and [98], the halogen atom represented by X is, for example, fluorine. Elemental atoms, iodine atoms, bromine atoms, iodine atoms and the like.

[0211] That is, in an appropriate solvent, 1.2 mol of NaH, KH or the like is used for 1 mol of the amino compound represented by the general formula [95], and the mixture is stirred and reacted at 20 to 140 ° C for 0.5 to 24 hours to form a metal salt. Then, formaldehyde-hydroxyalkyl tosylate and the like are added, and the mixture is stirred and reacted at 20 to 140 ° C. for 0.5 to 24 hours to produce a hydroxy compound represented by the general formula [96]. Then, to 1 mole of the hydroxy compound represented by the general formula [96], 1.2 moles of a halogenating agent (for example, triphenylphosphine and carbon tetrachloride, PC1, POC1, PC1, etc.) are added to the hydroxy compound. And 20 ~

3 3 5

The mixture was stirred and reacted at 140 ° C. for 0.5 to 24 hours to produce a halogenated product represented by the general formula [97]. This is dissolved without solvent or in a suitable solvent (for example, aromatic hydrocarbons such as toluene, xylene, and benzene, and ethers such as tetrahydrofuran and dioxane, for example). 1.5 mol of the imidazole compound represented by the general formula [93] is stirred and reacted at 20 to 140 ° C. for 0.5 to 24 hours, and the ionic liquid carrier of the present invention represented by the general formula [98] is supported. A halogen salt of the crowned ridge is obtained. The desired HX is reacted therewith to effect an aion exchange reaction to obtain the ionic liquid-carrying crowned conjugate of the present invention having the desired counter-on (X).

[0212] As the amino compound represented by the general formula [95], a commercially available amino compound or a compound appropriately synthesized according to a conventional method may be used.

[0213] The ionic liquid-supported crown conjugate represented by the general formula [1] of the present invention can be used as a catalyst for various synthetic reactions using a crown ether such as 18-crown-6 as a phase transfer catalyst. For example, various syntheses such as an acylylation reaction, a halogen substitution reaction, an ether synthesis reaction, a dehydrogenation, a hydrogenation reaction, a benzene sulfide formation reaction, a nucleophilic substitution reaction such as an ester synthesis reaction, an olefin isomerization reaction, and a reduction reaction. Can be used as a reaction catalyst

[0214] When the ionic liquid-carrying crown compound is used as a reaction catalyst (IL catalyst), 1 equivalent of the IL catalyst is dissolved in a reaction solvent, and a lithium salt, a sodium salt, Addition of 1.5 equivalents of a nucleophilic reagent which also has metal salt power such as potassium salt and cesium salt and 0.2 equivalents of a reaction substrate can be allowed to react to produce a desired reaction product.The obtained reaction product is, for example, getyl. Extract with organic solvents such as ether, ethyl acetate and toluene. It is obtained by doing.

[0215] The reaction solvent to be used is not particularly limited as long as it is usually used as a reaction solvent, but for the purpose of reuse, an ionic liquid is preferable. The ionic liquid is not particularly limited as long as it is usually used as an ionic liquid. Examples thereof include 1-ethyl-3-methylimidazolym methanesulfonate ([emim] [CH SO]), 1 -Ethyl-3-

3 4

Methylimidazolyl trifluoromethanesulfonate ([emim] [CF SO]), 1-ethyl

3 4

-3-methylimidazolidum bis (trifluoromethylsulfol) imidate ([emim] [(CF

Three

SO) N]), 1-ethyl-3-methylimidazolidium tetrafluoroborate ([emim] [BF]),

4 2 4

1-butyl-3-methylimidazolide hexafluorophosphate ([bmim] [PF]), 1-butyl

6

-3-methylimidazolym methanesulfonate ([bmim] [CH SO]), 1-butyl-3-methyl

3 4

Imidazolyl trifluoromethanesulfonate ([bmim] [CF SO]), 1-butyl-3-methyl

3 4

Louisimidazolyl bis (trifluoromethylsulfol) imidate ([bmim] [(CF SO) N])

3 4 2

, 1-butyl-3-methylimidazolidium tetrafluoroborate ([bmim] [BF]), 1-octy

Four

Le-3-methylimidazolidium hexafluorophosphate ([omim] [PF]), 1-ethyl-3-methyl

Five

Louisimidazolyme hexafluorophosphate ([emim] [PF]) and the like.

6

[0216] Further, the reaction solvent containing the IL catalyst into which the metal ion has been taken in after the reaction is completed is washed with water, whereby the metal ion taken into the IL catalyst can be easily removed. That is, since the activity of the IL catalyst is regenerated in this manner, the same reaction can be repeatedly performed by reusing the reaction solvent containing the IL catalyst. This recycling step is shown below. (Examples of the ionic liquid-supported crown compound according to the present invention include 1- (methyl-18-crown-6) -3-methyl-3H-imidazole-1-dimethylhexafluorophosphate. . }.

[0218] The ionic liquid-carrying crown conjugate of the present invention has the same properties as the conventional crown terrier conjugates such as 18-crown-6, but also in the reaction system despite expensive catalysts. It has a catalytic action similar to crown ether, which has the problem that it is difficult to recover and reuse it, and efficiently recovers the ionic liquid-carrying crown compound from the reaction system to regenerate the catalytic activity And can be reused.

[0219] 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.

Example

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.) is dissolved in 2 mL of carbon tetrachloride, and 630 mg (2.4%) of triphenylphosphine is added to the obtained solution. mmol) was added at room temperature under an argon atmosphere, and the mixture was stirred and reacted at 60 ° C. for 2 hours. After completion of the reaction, the solvent was removed from the obtained reaction solution, and the obtained crude product was purified by silica gel column chromatography (form: form / 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-imidazole-1-dium chloride

[0223] 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 obtained solution. Was added at room temperature, and the mixture was stirred and reacted 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:

'HNMR CCD C (0) CD) δ ppm: 4.43 (m, 23H), 4.96 (m, 3H), 5.44 (dd, J = 7, 13Hz,

3 3

1H), 5.65 (dd, J = 3, 13Hz, 1H), 8.89 (s, 2H), 10.99 (s, 1H).

¹³ CNMR (CD C (0) CD) 6 ppm: 36.73, 50.93, 70.13, 70.58, 70.99 (2C), 71.05 (2C),

3 3

71.26, 71.45 (2C), 71.53 (2C), 77.67, 123.96, 124.28, 139.13.

Example 2.1 Synthesis of 1- (methyl-18-crown-6) -3-methyl-3H-imidazole-1-dimethylhexafluorophosphate (IL catalyst)

[0226] In 3 mL of water, 1- (methyl-18-crown-6) -3-methyl-3H-imidazole-1-idum chloride (395 mg, l.OOmmol) obtained in Example 1 was dissolved. Then, 0.5 mL of a 60% aqueous solution of hexafluorophosphoric acid was slowly added to the obtained solution at room temperature, and the mixture was stirred and reacted for 5 hours. After completion of the reaction, the obtained reaction solution was extracted with 15 mL of methylene chloride, and the obtained organic layer was washed with water until neutral, to obtain 280 mg of the desired product as a yellow oil (yield: 71). %).

Physical property data:

'HNMR CCD C (0) CD) 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 = lHz, 1H), 7.66 (t, J = lHz, 1H), 8.95 (s, 1H). 1 3 CNMR (CD C (0) CD) 6 ppm: 36.45, 51.28, 69.65, 69.75, 70.63, 70.65,

3 3

70.70 (2C), 70.76 (2C), 71.08, 71.24, 71.47, 76.91, 123.54, 124.39, 138.06.

1 ⁹ FNMR (CD C (0) CD) δ ppm: 92.16 (d, J = 705Hz).

3 3

Comparative Example 1. Acylation reaction of benzyl chloride (without catalyst)

1-butyl-3-methylimidazolidin hexafluorophosphate ([bmim] [PF]) (this

6

[bmim] [PF] used was previously dried under reduced pressure at 80 ° C. for 5 hours. ) In 5mL,

6

85.5 mg (0.5 mmol) of sodium chloride was dissolved, 73.5 mg (0.75 mmol) of potassium acetate was added to the resulting solution at room temperature, and the mixture was stirred and reacted for 4 hours. After completion of the reaction, the desired product was extracted with 20 mL of ether. The same reaction was repeated four times using the remaining [bmim] [PF] solution. So

6

Table 1 shows the results.

Comparative Example 2. Acylation reaction of benzyl chloride (catalyst: 18-crown-6)

Other than using a solution of 26.4 mg (0.1 mmol) of 18-crown-6 in [bmim] [PF]

6

In the same manner as in Comparative Example 1, the desired product was obtained. The same reaction was repeated four times using the remaining solution. The results are also shown in Table 1.

Example 3. Acyridani Reaction of Benzyl Bromide (Catalyst: Compound of Example 2)

[bmim] [PF] solution (this [bmim] [PF] was previously dried under reduced pressure at 80 ° C for 5 hours.

6 6

It was. 5) In 5 mL, the tri (methyl-18-crown-6) -3-methyl-3H-imidazole-1-dimethylhexafluorophosphate (IL catalyst) obtained in Example 2 (50.0 mg, O.lmmol , 0.2 equivalents), and the resulting solution (IL catalyst-[bmim] [PF] solution) was added with 85.5 mg of benzyl bromide (

6

0.5 mmol) and 73.5 mg (0.75 mmol, 1.5 equivalents) of potassium acetate were added at room temperature, and the mixture was stirred and reacted for 1 hour. After the completion of the reaction, the desired product was extracted with 20 mL of ether. The remaining solution was added to 10 mL of dichloroethane, and after adding ImL of water, the mixture was stirred at room temperature for 1 hour to remove potassium ions incorporated in the IL catalyst [bmim] [PF] solution. 80 remaining solution

6

Drying under reduced pressure at 12 ° C. for 12 hours removed dichloroethane and water. The same reaction was repeated four times using the remaining IL catalyst [bmim] [PF] solution. The results are shown in Table 1.

6

I will show you.

[0230] [Table 1] Catalyst Reaction time Number of uses (Yield%)

(hr) 1 2 3 4 5 Example 3 IL catalyst 1> 98> 98 95 96 93 Comparative example 2 18 Crown 6 4 86 78 60 55 52 Comparative example 1 None 4 58 58 55 55 57

[0231] As is clear from the results in Table 1, the case where the acylidani reaction was carried out without using a catalyst (Comparative Example 1) or the case where the acylidani reaction was carried out using 18-crown-6 as a catalyst ( The use of the IL catalyst according to the present invention as a catalyst (Example 3) was higher than that of Comparative Example 2) in that the yield was higher even after several uses.

Examples 4 to 7. Acylation reaction of various bromides

[bmim] [PF] (5 mL) (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) contains various bromides (0.5 mmol),

6

A solution in which potassium carboxylate (0.75 mmol) and an IL catalyst (0.1 or 0.2 equivalent) were dissolved was stirred and reacted at room temperature, and the obtained product was extracted with 20 mL of getyl ether. Next, the solvent was removed to obtain various acylated products. The results are shown in Table 2.

[0233] [Table 2]

[0234] *. Group = acetyl group, Ph = phenyl group

As is evident from the results shown in Table 2, it was conducive to performing the acylylation reaction of various bromides using an IL catalyst as a catalyst, thereby obtaining various target products in high yield.

Example 8. Fluorination reaction of benzyl bromide (catalyst: IL catalyst)

The IL catalyst obtained in Example 2 was dissolved in 5 mL of [bmim] [PF] solution, and the resulting solution (I

6

Benzyl bromide 85.5mg (0.5mmol) and potassium fluoride on L catalyst [bmim] [PF] solution)

6

43.6 mg (0.75 mmol) was added, and the mixture was stirred and reacted at 80 ° C. for 10 hours. After the reaction was completed, 20 mL of getyl ether was added to the obtained reaction solution to extract benzyl fluoride. The remaining solution was dissolved in 10 mL of dichloroethane, and ImL of water was further added. The mixture was stirred at room temperature for 1 hour to remove potassium ions incorporated in the IL catalyst- [bmim] [PF] solution. Then, Was dried under reduced pressure at 80 ° C. for 12 hours to recover an IL catalyst— [bmim] [PF] solution.

6

Using this IL catalyst- [bmim] [PF] solution, the same reaction was repeated four times again. That

6

Table 3 shows the results.

Comparative Example 3. Fluorination reaction of benzyl bromide (catalyst: 18-crown-6)

Other than using a solution of 26.4 mg (0.1 mmol) of 18-crown-6 in [bmim] [PF]

6

Was performed in the same manner as in Example 8 to obtain benzyl fluoride. The same reaction was repeated twice using the remaining solution. The results are shown in Table 3.

[0237] [Table 3]

[0238] As is clear from the results in Table 3, the IL catalyst according to the present application (Example 8) was used more than when the fluorination reaction was performed using 18-crown-6 as the catalyst (Comparative Example 3). The other factor was that the yield was high even after several uses. In other words, when 18-crown-6 is used as a catalyst, the captured potassium ions cannot be removed, so that the yield decreases with each passing. In contrast, when the ionic liquid-carrying crown compound of the present invention is used, the captured potassium ions can be easily removed by washing with water. Obtained in yield.

Claims

The scope of the claims

General formula [1]

(Wherein, R ¹ is a group derived from a crown conjugate, R ² is a group derived from an ionic liquid, and T is an alkylene chain having 1 to 8 carbon atoms). The group derived from the crowny dagger represented by R ¹ is represented by the general formula [2]

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

― CH ₂ R ^U [3]

(Wherein, R ¹¹ represents a hydroxy group, an alkoxy group, an aralkyloxy group or an acyloxy group), and a group represented by the general formula [4]:

—— CHR ¹² CH ₂ R ¹ [4]

(In the formula, R ¹² and R ¹³ each independently represent a hydrogen atom, a hydroxy group, an alkoxy group or an acyloxy group, except that both R ¹² and R ¹³ are hydrogen atoms.) A group represented by the general formula [5]

—— C— R ¹⁴ [5]

0

[Wherein, R ¹⁴ represents a hydrogen atom, a hydroxy group, an alkyl group, an alkoxy group, an aryl group or an aryloxy group which may have an alkyl group as a substituent, or a general formula [6] R ¹⁵

— L [6] (Wherein, R ¹⁵ and R ^lb each independently represent an alkyl group). A to A and m A are each independently an oxygen atom, a sulfur atom or

1 3 4

Is the general formula [7] — R ¹⁷ [

(In the formula, R ¹⁷ has a bond bonding to T in the general formula [1], a hydrogen atom, an alkyl group, an alkylsulfur group, or an alkyl group as a substituent, and may be an aryl group. Or a benzenesulfol group or a heterocyclic group). However, any of R ^{3 to} R ⁸ , m R ⁹ , m R ^1G , and A to A and m A are represented by the general formula [7].

1 3 4

And only one of R ¹⁷ when it is a group to be bonded is a bond bonding to T in the general formula [1]. M represents an integer of 1 to 5, and R ³ and R ⁴ , R ⁵ and R ⁶ , R ⁷ and R ⁸ , and R ⁹ and R ^1G are each independently a cyclo with a carbon adjacent to each other. It may form a xane ring, a benzene ring or a naphthalene ring. The cyclohexane ring, benzene ring and naphthalene ring each independently represent an alkyl group, an alkenyl group, an acyl group, an acyloxy group, an alkoxycarbol group, a morpholmethyl group or a decahydronaphthyl group as a substituent. May be included. The ionic liquid-carrying crowned conjugate according to claim 1, wherein the compound is represented by the following formula:

A group represented by R ^{1 represented} by a crowny dagger is represented by the general formula [8]

(Wherein, R ^{18 to} R ²² , n R ²³ and n R ²⁴ are each independently a hydrogen atom, an alkyl group

, The general formula [3]

― CH ₂ R ^U [3]

(In the formula, R ¹¹ represents a hydroxy group, an alkoxy group, an aralkyloxy group or an acyloxy group. Represent. ), A general formula [4] CHR ¹² CH ₂ R ¹ [4]

— C— R ¹⁴ [5]

II

〇

― N, [6]

R ¹⁶

(Wherein, R ¹⁵ and R ¹⁶ each independently represent an alkyl group). A to A and n A are each independently an oxygen atom, a sulfur atom or

5 7 8

General formula [9]

N—R ²⁵ [9]

/

(In the formula, R ²⁵ represents a hydrogen atom, an alkyl group, an alkylsulfol group, an aryl group or a benzenesulfol group which may have an alkyl group as a substituent, or a heterocyclic group.) And n represents an integer of 1 to 5. In addition, 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 carbon adjacent to each other. The cyclohexane ring, benzene ring and naphthalene ring each independently represent an alkyl group, an alkenyl group, an acyl group, an acyloxy group, an alkoxycarbyl group, a morpholmethyl group or a decahydronaphthyl group. It may have a group. The ionic liquid-carrying crown compound according to claim 1, wherein the crown compound is represented by the following formula:

The group represented by R ¹ derived from the crowny dagger is represented by the general formula [10]

(Wherein, R ^{26 to} R ³¹ , p R ³² and p R ³³ are each independently a hydrogen atom, an alkyl group

, The general formula [3]

― CH ₂ R ^U [3]

—— CHR ¹² CH ₂ R ¹ [4]

— C— R ¹⁴ [5]

0

― N, [6]

R ¹⁶

(Wherein, R ¹⁵ and R ¹⁶ each independently represent an alkyl group). A, A and p of A are each independently an oxygen atom, a sulfur atom or

9 10 11

Is the general formula [9]

N—R ²⁵ [9]

/

(In the formula, R ²⁵ represents a hydrogen atom, an alkyl group, an alkylsulfol group, an aryl group or a benzenesulfol group which may have an alkyl group as a substituent, or a heterocyclic group. You. ), And p represents an integer of 1 to 5. R ²⁶ and R ²⁷ , R ²⁸ and R ²⁹ , R ^3G 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. It may be. The cyclohexane ring, benzene ring and naphthalene ring each independently represent, as a substituent, an alkyl group, an alkenyl group, an acyl group, an acyloxy group, an alkoxycarbyl group, a morpholmethyl group or a decahydronaphthyl group. It may have a group. The ionic liquid-carrying crowned conjugate according to claim 1, which is represented by}.

The group derived from the crowny conjugate represented by the general formula [8] is represented by the general formula [12]

5 8

]

(Wherein A to A and two A's are the same as described above).

5 7 8

Group or general formula [14]

(Wherein A to A and three A's are the same as described above) derived from the 18-crown-6 skeleton

5 7 8

The ionic liquid-carrying crown conjugate according to claim 3, which is a group.

A to A and 1 to 3 A in the general formulas [12] to [14] are oxygen atoms. 3. The ionic liquid-supported crowned conjugate according to 1.).

A group derived from a crowny conjugate represented by the general formula [8] is represented by the formula [19]

4. The ionic liquid-carrying crowned ridge according to claim 3, which is derived from 18-crown-6 represented by the formula:

[8] A group derived from the crowny conjugate represented by the general formula [10] is represented by the general formula [23]

(Wherein A to A are as defined above), a group derived from an aza-12-crown-4 skeleton,

9 11

Equation [24]

(Wherein, A, A and two A's are the same as described above.)

9 10 11

Group of origin or general formula [25]

(Wherein A, A and the three A's are the same as described above.) The ionic liquid-carrying crowny conjugate according to claim 4, which is a group derived from the ionic liquid.

[9] The claim wherein A, A and 1 to 3 A in the general formulas [23] to [25] are oxygen atoms.

9 10 11

9. The ionic liquid-carrying crowned ridge according to 8.

[10] The group derived from the crown compound represented by the general formula [10] is represented by the formula [30]

5. The ionic liquid-carrying crown compound according to claim 4, wherein the crown compound is derived from aza-18-crown-6 represented by the formula:

[11] The group derived from the ionic liquid represented by R ² is represented by the general formula [11] R ^{34 q} ® _{qX l} ^Q [HI

( ^Wherein , R ^{34q +} represents a quaternary ammonium ion or a quaternary phospho-ion ion having a valence of q, q X— represents a counter-one, and q represents 1 or 2). 2. The ionic liquid-carrying crowned conjugate according to claim 1, which is shown.

[12] ^{Quaternary ammonium} ion force represented by R ^{34q +} General formula [31]

R ³⁵

— NR ³⁷ [31]

R ³⁶

(In the formula, each of R ^{35 to} R ³⁷ independently represents a hydrogen atom, an alkyl group, an aralkyl group or an alkenyl group, provided that R ^{35 to} R ³⁷ are not hydrogen atoms.) Group, 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]

(In the formula, k R ^4Us each independently represent an alkyl group, and k represents an integer of 1 to 5) or a group represented by the general formula [34]:

(Wherein, R ⁴¹ represents an alkyl group). A quaternary ^{phosphonium ion} represented by R ^34qT is represented by the general formula [35]

R ³⁵

— _[35]

R ³⁶

The ionic liquid-carrying crown compound according to claim 11, which is a group represented by the formula (wherein, R ^{35 to} R ³⁷ are the same as described above).

X represents a halogen atom or hexafluorophosphoric acid, (HP F), tetrachloroaluminic acid (HA1C1), a general formula [36]

6 4

^{_{_{(R 42 S0 2) 2 NH}}} [36]

(Wherein, R ⁴² represents a haloalkyl group), a general formula [37]

(R ⁴ S0 ₂ ) ₃ CH [37]

(Wherein R ⁴³ represents a haloalkyl group), a general formula [38]

HB (R ⁴⁴ ) ₄ [38]

Wherein R ⁴⁴ represents a fluorine atom, a phenyl group or a cyano group which may have a haloalkyl group as a substituent, and a boric acid represented by the general formula [39]:

R ⁴⁵ S0 ₃ H [39]

(Wherein, R ⁴⁵ has an alkyl group, a haloalkyl group, or an alkyl group or a halogen atom as a substituent, and may also represent a phenyl group) or a sulfonic acid represented by the general formula [ 40] R ⁴⁶ COOH [40]

(In the formula, R ⁴⁶ has an alkyl group, a haloalkyl group, or an alkyl group or a halogen atom as a substituent, and may be a phenyl group.) 12. The ionic-carrying crowned conjugate according to claim 11, wherein:

The ionic liquid-carrying crown compound represented by the general formula [1] is converted to the general formula [52]

[In the formula, represents an alkyl group or an aralkyl group, R represents a hydrogen atom or an alkyl group, and A to A and the three As each independently represent an oxygen atom, a sulfur atom, or a general formula [9]

5 7 8

N—R ²⁵ [9]

/

(In the formula, R ²⁵ represents a hydrogen atom, an alkyl group, an alkylsulfol group, an aryl group or a benzenesulfol group which may have an alkyl group as a substituent, or a heterocyclic group.) X represents a counter-one; and T represents an alkylene chain having 1 to 8 carbon atoms. The ionic liquid-carrying crown compound according to claim 1, which is represented by the following formula:

[15] The ionic liquid-supported crown compound represented by the general formula [1] is converted to a ionic liquid-supported crown compound represented by the general formula [77]

[Wherein, R ^d represents an alkyl group or an aralkyl group, R represents a hydrogen atom or an alkyl group, and A, A, and three As each independently represent an oxygen atom, a sulfur atom, or a general formula [9 \ 1

/

(In the formula, R represents a hydrogen atom, an alkyl group, an alkylsulfol group, an aryl group or a benzenesulfol group which may have an alkyl group as a substituent, or a heterocyclic group.) X represents a counter-one; and T represents an alkylene chain having 1 to 8 carbon atoms. The ionic liquid-carrying crown compound according to claim 1, which is represented by the following formula:

[16] The general formula [52], wherein A to A and three A's are oxygen atoms.

5 7 8

An ionic liquid-supported crowned ridged product.

[17] In the general formula [52], T is a methylene group, R ³⁸ is a methyl group, R ³⁹ is a hydrogen atom, and X is hexafluorophosphoric acid-derived a-one (PF-). Claim 14

1 6

An ionic liquid-supported crowned ridged product.

[18] An ionic liquid-supported crown compound represented by the general formula [52] is represented by the formula [99]

15. The ionic liquid-supported crowned conjugate according to claim 14, which is represented by:

[19] A catalyst comprising the ionic liquid-supported crown compound according to claim 1.

[20] The catalyst according to claim 19, wherein the catalyst according to claim 19 is for a nucleophilic substitution reaction.