JP2006089463A - Method for producing aryl ether - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for the industrially advantageous production of aryl ethers. <P>SOLUTION: The aryl ether is produced by reacting an organic compound having one or more substituents to be subjected to nucleophilic substitution reaction with a phenolic compound in the presence of an alkyl-substituted imidazolium salt expressed by formula (1) (R<SP>1</SP>and R<SP>3</SP>are each independently a substituted or unsubstituted alkyl; R<SP>2</SP>, R<SP>4</SP>and R<SP>5</SP>are each independently H or a substituted or unsubstituted alkyl; Y<SP>-</SP>is a univalent anion excluding fluoride ion; and 0<n≤1). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for producing aryl ethers.

  Aryl ethers are extremely important compounds as various chemical products including medicinal and agricultural chemicals, electronic materials, and synthetic intermediates thereof (see, for example, Patent Document 1 and Non-Patent Document 1).

  Various methods for synthesizing aryl ethers using a nucleophilic substitution reaction have been developed. For example, a method of heating 4-nitrofluorobenzene and sodium phenolate in anhydrous dimethyl sulfoxide in the presence of phosphazenium chloride (see, for example, Patent Document 1), nitro-substituted halobenzenes and phenolates. A method of heating in liquid ammonia under pressure (for example, see Patent Document 2), a method of isolating sodium phenolates and then heating with halopyridines in dimethylformamide (for example, see Patent Document 3). A method of heating cyano-substituted halobenzenes and phenols in an aprotic polar solvent in the presence of potassium fluoride-alumina and 18-crown-6 (see, for example, Non-Patent Document 1), 4-nitrohalo. A method of heating benzene and phenols using microwaves in the presence of a base (for example, Patent Document 2), a method of reacting a phenol and an alkyl halide in the presence of a strong base and a quaternary basic salt while performing azeotropic dehydration (for example, refer to Patent Document 4), cesium fluoride-celite. A method of reacting a phenol with an alkyl halide in the presence of (for example, refer to Non-patent Document 3), in a mixed solvent of an ionic liquid and water, phenol and benzyl bromide in the presence of an excessive amount of a strong base. (For example, refer nonpatent literature 4.) etc. are known. However, all of these include industrial use such as expensive reaction reagents and compounds that are problematic in handling, special equipment is required, and substrates having substituents that are unstable to bases cannot be used. It could not be said that it was sufficient as a general manufacturing method.

Japanese Patent Laid-Open No. 2002-3427 Japanese Patent Publication No. 6-86410 French Published Patent No. 1527714 JP-A-6-128185 J. Org. Chem., 63, 6338 (1998) Eur.J.Org.Chem., 1278 (2002) Tetrahedron Lett., 43,8603 (2002) Tetrahedron, 59,789 (2003)

  Therefore, the present inventor has intensively studied to develop an industrially more advantageous method for producing aryl ethers. As a result, the reaction between an organic compound having one or more substituents that undergo a nucleophilic substitution reaction and a phenol is performed. It has been found that aryl ethers can be efficiently produced even under neutral to weakly basic conditions when carried out in the presence of an alkyl-substituted imidazolium salt containing a fluoride ion that can be recycled. It has been found that the reaction proceeds efficiently even when the amount of the alkyl-substituted imidazolium salt containing fluoride ions is reduced when used in combination with a base, and the present invention has been achieved.

（式中、Ｒ^１およびＲ^３は、それぞれ同一または相異なって、置換もしくは無置換のアルキル基を表し、Ｒ^２、Ｒ^４およびＲ^５はそれぞれ同一または相異なって、水素原子または置換もしくは無置換のアルキル基を表す。Ｙ⁻はフッ化物イオンを除く１価のアニオンを表す。また、０＜ｘ≦１である。）
で示されるフッ化物イオンを含有するアルキル置換イミダゾリウム塩の存在下に、求核置換反応を受ける置換基を１または２以上有する有機化合物とフェノール類とを作用させることを特徴とするアリールエーテル類の製造方法を提供するものである。 That is, the present invention provides the formula (1)

(Wherein R ¹ and R ³ are the same or different and each represents a substituted or unsubstituted alkyl group; R ² , R ⁴ and R ⁵ are the same or different and each represents a hydrogen atom or substituted or unsubstituted; .Y to represent a substituted alkyl group ^- represents a monovalent anion other than a fluoride ion also is a 0 <x ≦ 1)..
Aryl ethers characterized in that an organic compound having one or more substituents undergoing a nucleophilic substitution reaction and a phenol are allowed to act in the presence of an alkyl-substituted imidazolium salt containing a fluoride ion represented by The manufacturing method of this is provided.

  According to the present invention, aryl ethers can be produced efficiently and inexpensively under relatively mild conditions without using a compound having a problem in handling or a special apparatus, which is industrially advantageous. In addition, the alkyl-substituted imidazolium salt containing a fluoride ion of the present invention itself has the property of an ionic liquid, so that it can be easily recovered and reused. Further, in the above formula (1), x Since the melting point can be lowered to room temperature or less by appropriately selecting, the reaction can be carried out under a wide range of temperature conditions, which is advantageous in terms of industrial handling and environment.

  First, an alkyl-substituted imidazolium salt containing a fluoride ion represented by the above formula (1) (hereinafter abbreviated as imidazolium salt (1)) will be described.

In the formula, R ¹ and R ³ are the same or different and each represents a substituted or unsubstituted alkyl group; R ² , R ⁴ and R ⁵ are the same or different and each represents a hydrogen atom or substituted or unsubstituted. Represents a good alkyl group.

Examples of the unsubstituted alkyl group represented by R ^{1 to} R ⁵ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a decyl group, Examples thereof include linear, branched or cyclic alkyl groups having 1 to 10 carbon atoms such as cyclopropyl group, 2,2-dimethylcyclopropyl group, cyclopentyl group, cyclohexyl group and menthyl group.

  Examples of the substituent that may be present on the alkyl group include a substituted or unsubstituted aryl group described later, a substituted or unsubstituted alkoxy group described later, a substituted or unsubstituted aryloxy group described later, and a later described Examples thereof include a substituted or unsubstituted alkylcarbonyl group, a substituted or unsubstituted arylcarbonyl group described later, a carboxy group, and a fluorine atom. Specific examples of the substituted alkyl group include, for example, a fluoromethyl group, a trifluoromethyl group, a methoxymethyl group, an ethoxymethyl group, a methoxyethyl group, a benzyl group, a 4-fluorobenzyl group, a 4-methylbenzyl group, a phenoxymethyl group, Examples include 2-oxopropyl group, 2-oxobutyl group, phenacyl group, 2-carboxyethyl group and the like.

  As an unsubstituted aryl group, C6-C10 hydrocarbon aromatic groups, such as a phenyl group and a naphthyl group, are mentioned, for example. Examples of the substituent that may be present on the aryl group include, for example, the substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group described later, an aryl group, a substituted or unsubstituted aryloxy group described later, Examples thereof include a substituted or unsubstituted alkylcarbonyl group described later, a substituted or unsubstituted arylcarbonyl group described later, a carboxy group, a fluorine atom, and the like. Specific examples of the substituted aryl group include a 4-methylphenyl group and a 4-methoxyphenyl group.

  Examples of the alkyl group in the substituted or unsubstituted alkoxy group include the substituted or unsubstituted alkyl group. Specific examples of the substituted or unsubstituted alkoxy group include, for example, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, trifluoromethoxy group, benzyloxy Group, 4-methylbenzyloxy group, 4-methoxybenzyloxy group, 3-phenoxybenzyloxy group and the like.

  Examples of the aryl group in the substituted or unsubstituted aryloxy group include the substituted or unsubstituted aryl group. Specific examples of the substituted or unsubstituted aryloxy group include a phenoxy group, 2-methylphenoxy group, 4-methylphenoxy group, 4-methoxyphenoxy group, 3-phenoxyphenoxy group, and the like.

  Examples of the alkyl group in the substituted or unsubstituted alkylcarbonyl group include the substituted or unsubstituted alkyl group. Examples of the substituted or unsubstituted alkylcarbonyl group include an acetyl group, a propionyl group, a benzylcarbonyl group, a 4-methylbenzylcarbonyl group, and a 4-methoxybenzylcarbonyl group.

  Examples of the aryl group in the substituted or unsubstituted arylcarbonyl group include the substituted or unsubstituted aryl group. Examples of the substituted or unsubstituted arylcarbonyl group include a benzoyl group, a 2-methylbenzoyl group, a 4-methylbenzoyl group, and a 4-methoxybenzoyl group.

Y ⁻ represents a monovalent anion excluding fluoride ions, for example, halide ions excluding fluoride ions such as chloride ions, bromide ions, iodide ions; borate ions such as tetrafluoroborate anions; Phosphate ions such as hexafluorophosphate anion; antimonate ions such as hexafluoroantimonate anion; sulfonate ions such as trifluoromethanesulfonate anion; amide ions such as bis (trifluoromethanesulfonyl) amide anion; Etc.

  x represents a ratio of fluoride ions to all anions contained in the imidazolium salt (1), and can be arbitrarily selected within the range of 0 <x ≦ 1. When x is close to 0, the efficiency as an activator of the nucleophilic substitution reaction is lowered, and therefore a range of about 0.4 <x ≦ 1 is preferable.

  As such imidazolium salt (1), when x = 1, for example, 1,3-dimethylimidazolium fluoride, 1,2,3-trimethylimidazolium fluoride, 1,2,3,4-tetramethyl Imidazolium fluoride, 1,2,3,4,5-pentamethylimidazolium fluoride, 1-methyl-3-ethylimidazolium fluoride, 1,2-dimethyl-3-ethylimidazolium fluoride, 1, 3-diethylimidazolium fluoride, 1-methyl-3-propylimidazolium fluoride, 1-methyl-3-butylimidazolium fluoride, 1,2-dimethyl-3-butylimidazolium fluoride, 1-methyl- 3-pentylimidazolium fluoride, 1-methyl-3-hexylimidazolium Fluoride, 1,3-dimethyl-2-ethylimidazolium fluoride, 1,3-dimethyl-2-propylimidazolium fluoride, 1,3-dimethyl-2-butylimidazolium fluoride, 1-dodecyl-2- Methyl-3-dodecylimidazolium fluoride, 1-ethoxymethyl-3-methylimidazolium fluoride, 1-trifluoromethyl-3-methylimidazolium fluoride, 1-dodecyl-2-methyl-3-benzylimidazolium fluoride And alkyl-substituted imidazolium fluorides such as rides. In the case of 0 <x <1, for example, some of the fluoride ions of the alkyl-substituted imidazolium fluorides are chloride ions, bromide ions, iodide ions, respectively. Tetrafluoroborate anion Hexafluorophosphate anion, hexafluoroantimonate anion, trifluoromethanesulfonic acid anion, mixed alkyl-substituted imidazolium salt is replaced by bis (trifluoromethanesulfonyl) amide anion and the like.

  These may form a complex with a compound inactive to nucleophilic substitution reaction such as water or polar solvent.

  The imidazolium salt (1) is produced using a method such as a salt exchange reaction between a fluoride such as silver fluoride or potassium fluoride and an alkyl-substituted imidazolium salt where x = 0 in the above formula (1). can do. Moreover, you may prepare by mixing the alkyl substituted imidazolium salt which is x = 0 in the said Formula (1), and the alkyl substituted imidazolium fluoride which is x = 1.

  Next, the reaction between an organic compound having one or more substituents that undergo a nucleophilic substitution reaction and phenols in the presence of the imidazolium salt (1) will be described.

Examples of organic compounds having one or more substituents that undergo a nucleophilic substitution reaction include:
An organic compound in which one or more hydrogen atoms on a substituted or unsubstituted aromatic compound are substituted with a substituent that undergoes a nucleophilic substitution reaction;
An organic compound in which one or more hydrogen atoms on a substituted or unsubstituted saturated hydrocarbon are substituted with a substituent that undergoes a nucleophilic substitution reaction;
And according to the reaction of the present invention, respectively,
Diaryl ethers in which one or more hydrogen atoms on a substituted or unsubstituted aromatic compound are substituted with an aryloxy group or an arylthio group;
Alkylaryl ethers in which one or more hydrogen atoms on a substituted or unsubstituted saturated hydrocarbon are substituted with an aryloxy group or an arylthio group;
Is obtained.

  Examples of the aromatic compound having one or more substituents that undergo a nucleophilic substitution reaction include hydrocarbon aromatic rings such as benzene ring and naphthalene ring or heteroaromatic rings such as pyridine ring, pyrimidine ring and quinoline ring. The substituent is not particularly limited as long as at least one substituent that undergoes a nucleophilic substitution reaction is bonded thereto, and may have a substituent other than the substituent that undergoes a nucleophilic substitution reaction on these aromatic rings.

  Examples of the saturated hydrocarbon having one or more substituents that undergo a nucleophilic substitution reaction include methane, ethane, propane, butane, isobutane, pentane, decane, cyclopropane, 2,2-dimethylcyclopropane, cyclopentane, and cyclohexane. It is not particularly limited as long as a substituent that undergoes at least one nucleophilic substitution reaction is bonded to a linear, branched, or cyclic saturated hydrocarbon having 1 to 10 carbon atoms such as saturated hydrocarbon. It may have a substituent other than a substituent that undergoes a nucleophilic substitution reaction.

（式中、Ｒは置換もしくは無置換のアリール基または置換もしくは無置換のアルキル基を表し、Ｚはハロゲン原子、ニトロ基、スルホ基、置換もしくは無置換のアルキルスルホニルオキシ基、置換もしくは無置換のアリールスルホニルオキシ基、置換もしくは無置換のアルキルカルボニルオキシ基または置換もしくは無置換のアリールカルボニルオキシ基を表す。）
で示される化合物（以下、有機化合物（２）と略記する。）が挙げられる。 Examples of organic compounds having one or more substituents that undergo such nucleophilic substitution reactions include those of the formula (2)

(In the formula, R represents a substituted or unsubstituted aryl group or a substituted or unsubstituted alkyl group; Z represents a halogen atom, a nitro group, a sulfo group, a substituted or unsubstituted alkylsulfonyloxy group, a substituted or unsubstituted group; Represents an arylsulfonyloxy group, a substituted or unsubstituted alkylcarbonyloxy group or a substituted or unsubstituted arylcarbonyloxy group.)
(Hereinafter abbreviated as organic compound (2)).

  Examples of the unsubstituted aryl group represented by R include C6-C10 hydrocarbon aromatic groups such as phenyl and naphthyl groups, and C4-C10 such as pyridyl, pyrimidyl and quinolyl groups. Heteroaromatic groups can be mentioned.

  Examples of the substituent that may be present on the aryl group include an aryl group, a substituted or unsubstituted alkyl group described later, a substituted or unsubstituted alkoxy group described later, and a substituted or unsubstituted aryloxy group described later. Examples thereof include a substituted or unsubstituted alkylcarbonyl group described later, a substituted or unsubstituted arylcarbonyl group described later, a trihalomethyl group, a carboxy group, a sulfamoyl group, a cyano group, and a carbamoyl group. Of these substituents, adjacent substituents may be bonded to each other to form a ring together with the bonded carbon atoms. Specific examples of the substituted aryl group include a 2-methylphenyl group, a 4-methylphenyl group, a 4-methoxyphenyl group, and a 3-phenoxyphenyl group.

  Examples of the unsubstituted alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, decyl group, cyclopropyl group, 2,2- Examples thereof include linear, branched or cyclic alkyl groups having 1 to 10 carbon atoms such as dimethylcyclopropyl group, cyclopentyl group, cyclohexyl group and menthyl group. Examples of the substituent which may be present on the alkyl group include a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom, the substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group described later, and a later-described substituent group. Examples thereof include a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylcarbonyl group described later, a substituted or unsubstituted arylcarbonyl group described later, a carboxy group, a sulfamoyl group, a cyano group, and a carbamoyl group. Specific examples of the substituted alkyl group include methoxymethyl group, ethoxymethyl group, methoxyethyl group, benzyl group, 4-methoxybenzyl group, 3-phenoxybenzyl group, phenylethyl group, naphthylpropyl group, benzoylmethyl group, 4 -A methyl benzoylmethyl group etc. are mentioned.

  Examples of the alkyl group in the substituted or unsubstituted alkoxy group include the substituted or unsubstituted alkyl group. Specific examples of the substituted or unsubstituted alkoxy group include, for example, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, decyloxy group, Cyclopentyloxy group, cyclohexyloxy group, menthyloxy group, methoxymethoxy group, ethoxymethoxy group, methoxyethoxy group, benzyloxy group, 4-methylbenzyloxy group, 4-methoxybenzyloxy group, 3-phenoxybenzyloxy group, etc. Can be mentioned.

  Examples of the aryl group in the substituted or unsubstituted aryloxy group include the substituted or unsubstituted aryl group. Specific examples of the substituted or unsubstituted aryloxy group include a phenoxy group, 2-methylphenoxy group, 4-methylphenoxy group, 4-methoxyphenoxy group, 3-phenoxyphenoxy group, and the like.

  Examples of the alkyl group in the substituted or unsubstituted alkylcarbonyl group include the substituted or unsubstituted alkyl group. Specific examples of the substituted or unsubstituted alkylcarbonyl group include an acetyl group, a propionyl group, a benzylcarbonyl group, a 4-methylbenzylcarbonyl group, and a 4-methoxybenzylcarbonyl group.

  Examples of the aryl group in the substituted or unsubstituted arylcarbonyl group include the substituted or unsubstituted aryl group. Specific examples of the substituted or unsubstituted arylcarbonyl group include a benzoyl group, a 2-methylbenzoyl group, a 4-methylbenzoyl group, and a 4-methoxybenzoyl group.

  The trihalomethyl group is a substituent in which all hydrogen atoms on the methyl group are substituted with halogen atoms such as a fluorine atom and a chlorine atom. For example, a trifluoromethyl group, a trichloromethyl group, a difluorochloromethyl group, a dichloro A fluoromethyl group etc. are mentioned.

  Examples of the unsubstituted alkyl group represented by R include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, decyl group, cyclopropyl group, Examples thereof include linear, branched or cyclic alkyl groups having 1 to 10 carbon atoms such as 2,2-dimethylcyclopropyl group, cyclopentyl group, cyclohexyl group and menthyl group.

  Examples of the substituent that may be present on the alkyl group include the substituted or unsubstituted aryl group, the substituted or unsubstituted alkoxy group, the substituted or unsubstituted aryloxy group, and the substituted or unsubstituted group. And the above-mentioned alkylcarbonyl group, substituted or unsubstituted arylcarbonyl group, carboxy group, sulfamoyl group, cyano group, carbamoyl group and the like. Of these substituents, adjacent substituents may be bonded to each other to form a ring together with the bonded carbon atoms. Specific examples of the substituted alkyl group include methoxymethyl group, ethoxymethyl group, methoxyethyl group, benzyl group, 4-methoxybenzyl group, 3-phenoxybenzyl group, phenylethyl group, naphthylpropyl group, benzoylmethyl group, 4 -A methyl benzoylmethyl group etc. are mentioned.

  Examples of the substituent that undergoes the nucleophilic substitution reaction include a halogen atom, a nitro group, a sulfo group, a substituted or unsubstituted alkylsulfonyloxy group, a substituted or unsubstituted arylsulfonyloxy group, and a substituted or unsubstituted alkylcarbonyloxy group. Or a substituted or unsubstituted arylcarbonyloxy group etc. are mentioned. When two or more such substituents are present, they may be the same as or different from each other.

  Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the substituted or unsubstituted alkylsulfonyloxy group include a methanesulfonyloxy group, an ethanesulfonyloxy group, and a trifluoromethanesulfonyloxy group. Examples of the substituted or unsubstituted arylsulfonyloxy group include a paratoluenesulfonyloxy group, a benzenesulfonyloxy group, and a 1-naphthalenesulfonyloxy group, and examples of the substituted or unsubstituted alkylcarbonyloxy group include Is, for example, a trifluoroacetoxy group, a pentafluoroethanecarbonyloxy group, etc. The substituted or unsubstituted arylcarbonyloxy group is, for example, a 2,3,5,6-tetrafluorobenzoyloxy group Benzoylamino group and the like.

  Among organic compounds having one or more substituents that undergo such a nucleophilic substitution reaction, examples of aromatic compounds include 4-chloronitrobenzene, 4-bromonitrobenzene, 4-fluoronitrobenzene, 2-chloronitrobenzene, 2-bromo. Nitrobenzene, 2-fluoronitrobenzene, 4-cyanochlorobenzene, 4-cyanobromobenzene, 4-chloro-3-nitrobenzonitrile, 4-methyl-2-bromofluorobenzene, methyl 2-nitro-5-chlorobenzoate, 4 -Trifluoromethyl-2-chlorofluorobenzene, 4-trifluoromethyl-1,2-dichlorobenzene, 2-chloro-3-nitrobenzonitrile, 2-cyanofluorobenzene, 4-cyanofluorobenzene, 2,6- Difluorocyanobenzene, 3,4- Fluorocyanobenzene, 1-chloro-2,4-dinitrobenzene, tetrachloroterephthalonitrile, tetrafluoroterephthalonitrile, tetrachloroorthophthalonitrile, 1,3-dichloro-4,6-dinitrobenzene, 3,5- Dichloro-4-fluoronitrobenzene, 1,3,5-trichlorobenzene, 1,3,4-trichlorobenzene, 1,3,5-trifluorobenzene, 1,2,4-trifluorobenzene, 3,4-difluoro Chlorobenzene, 2-chloro-5-nitropyridine, 2-chloro-5-trifluoromethylpyridine, 2-chloro-3-nitropyridine, 2-chloro-3-trifluoromethylpyridine, 2,3-dichloro-5 Trifluoromethylpyridine, 2,6-dichloropyridine, 2,6-dibromopi Gin, 2-chloroquinoline, 4-bromoquinoline, 4,8-dichloroquinoline, 4,6-dichloropyrimidine, 4,6-difluoropyrimidine, 4,5,6-trichloropyrimidine, 4,5,6-trifluoro Examples include pyrimidine and 2-chloro-4,6-dimethoxypyrimidine.

  Examples of the saturated hydrocarbon having one or more substituents that undergo a nucleophilic substitution fluorination reaction include 1-chlorobutane, 1-bromobutane, 1-iodobutane, 1-chlorocyclobutane, 1-chloropentane, 1-bromo. Pentane, 1-chlorocyclopentane, 1-chloro-4-bromobutane, 1-chlorohexane, 1-bromohexane, 1,6-dibromohexane, 1-chloroheptane, 1-bromoheptane, 2-chloroheptane, 2 -Bromoheptane, 1-chlorooctane, 1-bromooctane, 2-chlorooctane, 2-bromooctane, benzyl chloride, benzyl bromide, (1-chloroethyl) benzene, (1-bromoethyl) benzene, 4-methoxybenzyl chloride, 4-methylbenzyl bromide, 3,4,5-to Fluorobenzyl bromide, butyl paratoluenesulfonate, butyl methanesulfonate, pentyl paratoluenesulfonate, pentyl methanesulfonate, hexyl paratoluenesulfonate, hexyl methanesulfonate, heptyl paratoluenesulfonate, heptyl methanesulfonate, paratoluene Examples include octyl sulfonate, octyl methanesulfonate, butyl trifluoroacetate, butyl 2,3,5,6-tetrafluorobenzoate, and octyl trifluoroacetate.

  As the organic compound having one or two or more substituents that undergo the nucleophilic substitution fluorination reaction, commercially available ones may be used, or those produced according to various known reactions may be used.

  When using an organic compound having two or more substituents that undergo a nucleophilic substitution reaction, only one substituent may react depending on the reaction conditions, or all or part of the two or more substituents react. There is also. When an aromatic compound having two or more substituents that undergo a nucleophilic substitution reaction is used, the following reactivity is usually exhibited, and only the most reactive substituent may react.

  In an aromatic compound having one or more substituents that undergo a nucleophilic substitution reaction, when the substituted or unsubstituted aromatic compound is a hydrocarbon-based aromatic compound, it is usually electron-withdrawing at the para-position or ortho-position. A substituent that undergoes a nucleophilic substitution reaction having a substituent is preferentially substituted with an aryloxy group or an arylthio group. Examples of the electron-withdrawing substituent include a substituted or unsubstituted alkylcarbonyl group, a substituted or unsubstituted arylcarbonyl group, a trihalomethyl group, a carboxy group, a sulfamoyl group, and a cyano group. For example, in the reaction of 4-chloronitrobenzene, both a chlorine atom and a nitro group undergo a nucleophilic substitution reaction, but a chlorine atom having a nitro group with a higher electron-withdrawing property at the para position is preferentially substituted. Usually, 4-aryloxynitrobenzene or 4-arylthionitrobenzene is selectively produced.

  Further, in an aromatic compound having one or more substituents that undergo a nucleophilic substitution reaction, when the substituted or unsubstituted aromatic compound is a heteroaromatic compound, usually the heteroatoms constituting the heteroaromatic ring A substituent that undergoes a nucleophilic substitution reaction bonded to the α-position or the γ-position is preferentially substituted with an aryloxy group or an arylthio group. For example, in 2-chloro-3-nitropyridine, the chlorine atom at the 2-position is usually preferentially substituted to selectively produce 2-aryloxy-3-nitropyridine or 2-arylthio-3-nitropyridine. In addition, when a substituent that undergoes a nucleophilic substitution reaction is bonded to both the α-position and the γ-position, only the substituent at the α-position may react depending on the influence of other substituents or reaction conditions. Only the substituent at the γ position may react. Of course, substituents at both positions may react.

  The phenol is not particularly limited as long as it is an aromatic compound in which one or two or more hydrogen atoms on a substituted or unsubstituted aromatic compound are substituted with an —OH group or an —SH group.

  Aromatic compounds include, for example, those in which a substituent that undergoes at least one nucleophilic substitution reaction is bonded to a hydrocarbon aromatic ring such as a benzene ring or a naphthalene ring or a heteroaromatic ring such as a pyridine ring or a quinoline ring. If it does not specifically limit, you may have substituents other than -OH group or -SH group on these aromatic rings.

（式中、Ａｒは置換もしくは無置換のアリール基を表し、Ｑは酸素原子または硫黄原子を表す。）
で示される化合物（以下、フェノール類（３）と略記する。）が挙げられる。 As such phenols, for example, the formula (3)

(In the formula, Ar represents a substituted or unsubstituted aryl group, and Q represents an oxygen atom or a sulfur atom.)
(Hereinafter abbreviated as phenols (3)).

  Examples of the unsubstituted aryl group represented by Ar include aromatic groups having 6 to 10 carbon atoms such as phenyl group and naphthyl group, and heteroaromatic groups having 4 to 10 carbon atoms such as pyridyl group and quinolyl group. It is done.

  Examples of the substituent that may be present on the aryl group include a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted aryloxy. Group, substituted or unsubstituted alkylcarbonyl group, substituted or unsubstituted arylcarbonyl group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, trihalomethyl group, carboxy group, formyl group, sulfo group Sulfamoyl group, cyano group, nitro group, amino group, carbamoyl group and the like. Of these substituents, adjacent substituents may be bonded to each other to form a ring together with the bonded carbon atoms.

  Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.

  Substituted or unsubstituted alkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted alkylcarbonyl group, substituted or unsubstituted arylcarbonyl group Examples of the trihalomethyl group include the same substituents as those exemplified as the substituent that may be present on the aryl group of the organic compound having one or more substituents that undergo a nucleophilic substitution reaction.

  The alkyl group in the substituted or unsubstituted alkylsulfonyl group and the aryl group in the substituted or unsubstituted arylsulfonyl group have an aryl group of an organic compound having one or more substituents that undergo a nucleophilic substitution reaction. The substituted or unsubstituted alkyl group and the substituted or unsubstituted aryl group exemplified as the substituents that may be used are exemplified. Specific examples of the substituted or unsubstituted alkylsulfonyl group and the substituted or unsubstituted arylsulfonyl group include a methylsulfonyl group and a phenylsulfonyl group.

  Examples of such phenols include phenol, o-cresol, m-cresol, p-cresol, 2-fluorophenol, 3-fluorophenol, 4-fluorophenol, 2-chlorophenol, 3-chlorophenol, and 4-chlorophenol. 2-bromophenol, 3-bromophenol, 4-bromophenol, 2,4-dichlorophenol, 2,5-dichlorophenol, 3,5-dichlorophenol, 2,4-difluorophenol, 3,5-difluorophenol , 2-chloro-4-fluorophenol, 4-trifluoromethylphenol, 2-methoxyphenol, 3-methoxyphenol, 4-methoxyphenol, 2-ethoxyphenol, 3-ethoxyphenol, 4-ethoxyphenol, catechol Resorcinol, hydroquinone, 4-nitrophenol, 4-phenylphenol, 4-phenoxyphenol, 3-phenoxyphenol, vanillin, thiophenol, 1-naphthol, 2-naphthol, 1-thionaphthol, 2-methylthiophenol, 4-chloro Thiophenol, 2-fluorothiophenol, 2-hydroxypyridine, 4-hydroxypyridine, 3-hydroxypyridine, 4,6-dihydroxypyrimidine, 4-hydroxyquinazoline, 4,4'-dihydroxydiphenyl ether, 4,2'-dihydroxy Examples include diphenyl ether and 2,2′-dihydroxydiphenyl ether.

  As these phenols, commercially available products may be used, or those produced according to known methods may be used.

  When phenols having two or more —OH groups or —SH groups are used as phenols, only one —OH group or —SH group may react depending on the reaction conditions, or two or more —OH groups may be reacted. Alternatively, all or a part of the —SH group may react.

  The amount of phenol used is the —OH group or —SH group desired for the reaction on the phenol relative to the substituent desired for the reaction on the organic compound having one or more substituents that undergo the nucleophilic substitution reaction. If used on the basis of about 1 mole, the object of the present invention can be usually achieved. When it has only one substituent that undergoes a nucleophilic substitution reaction, it is preferably in the range of 1 to 5 moles from the viewpoint of reaction efficiency. Moreover, when it has two or more substituents which receive a nucleophilic substitution reaction, what is necessary is just to set the usage-amount within the range from which the substituent which does not desire a reaction does not receive a nucleophilic substitution reaction based on the said priority of the reactivity.

  The amount of the imidazolium salt (1) used is usually 1 mol times or more based on fluoride ions with respect to the substituent desired to be reacted on the organic compound having one or more substituents that undergo a nucleophilic substitution reaction. . Although there is no upper limit in particular, when it has only one substituent which undergoes a nucleophilic substitution reaction, it is preferably in the range of 1 to 5 moles from the viewpoint of reaction efficiency. Moreover, when it has two or more substituents which receive a nucleophilic substitution reaction, what is necessary is just to set the usage-amount within the range from which the substituent which does not desire a reaction does not receive a nucleophilic substitution reaction based on the said priority of the reactivity.

  This reaction can be carried out in the presence of an organic solvent or can be carried out without a solvent.

  The organic solvent in the case of carrying out using a solvent is not particularly limited as long as it is inactive to the reaction. For example, ether solvents such as methyl tert-butyl ether, tetrahydrofuran, diglyme; acetonitrile, propionitrile, etc. Nitrile solvents; aromatic hydrocarbon solvents such as toluene and xylene; amide solvents such as dimethylformamide and dimethylacetamide; sulfur-containing solvents such as sulfolane and dimethylsulfoxide;

  When a solvent is used, the amount used is not particularly limited, but considering volumetric efficiency and the like, it is practically 100 weight times or less with respect to the imidazolium salt (1). The reaction temperature is usually in the range of -20 to 200 ° C.

  In this reaction, the use amount of the imidazolium salt (1) can be reduced by using an inorganic base as necessary. Examples of the inorganic base include alkali metal or alkaline earth metal carbonates, hydrogen carbonates, hydroxides, and the like. Specifically, carbonates such as lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, magnesium carbonate, calcium carbonate; lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, cesium hydrogen carbonate, magnesium hydrogen carbonate, calcium hydrogen carbonate Bicarbonates such as lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide; and any mixtures thereof. Preferably carbonates are used.

  The amount of the inorganic base used is not particularly limited, but in order to effectively reduce the amount of the imidazolium salt (1) used, the reaction on the organic compound having one or more substituents that undergo a nucleophilic substitution reaction is performed. It is usually used in an amount of 1 mole or more with respect to the desired substituent. The upper limit is not particularly limited, but the operability and economical efficiency are deteriorated even if it is used in many amounts.

  The amount of imidazolium salt (1) used when such an inorganic base is used is based on fluoride ions relative to the substituent desired for the reaction on the organic compound having one or more substituents that undergo a nucleophilic substitution reaction. Usually, it is 0.01 mol times or more. Although there is no upper limit in particular, when it has only one substituent which undergoes a nucleophilic substitution reaction, it is preferably in the range of 0.1 to 1 mole times from the viewpoint of reaction efficiency. Moreover, when it has two or more substituents which receive a nucleophilic substitution reaction, what is necessary is just to set the usage-amount within the range from which the substituent which does not desire a reaction does not receive a nucleophilic substitution reaction based on the said priority of the reactivity.

  The mixing order of the reaction reagents is not particularly limited when mixing at a reaction temperature or lower. When mixing under reaction temperature conditions, if necessary, an organic compound having one or more substituents that undergo a nucleophilic substitution reaction in a mixture of phenols and imidazolium salt (1) coexisting with a solvent or an inorganic base Is preferably added.

  This reaction may be carried out under normal pressure conditions or under pressurized conditions. In addition, the progress of the reaction can be confirmed by ordinary analysis means such as gas chromatography, high performance liquid chromatography, thin layer chromatography, NMR, IR and the like.

（式中、Ｒ、ＱおよびＡｒは、それぞれ前記と同一の意味を表す。）
で示される化合物が得られる。 The main product of this reaction is aryl ethers. For example, if an organic compound (2) and a phenol (3) are reacted, the formula (4)

(In the formula, R, Q and Ar each have the same meaning as described above.)
Is obtained.

  After completion of the reaction, crystallization treatment, distillation treatment, etc. are carried out, and if necessary, water and / or an organic solvent insoluble in water is added, extraction treatment is performed, and the resulting organic layer is concentrated. Ethers can be isolated. The obtained aryl ethers may be further purified, for example, by means such as distillation or column chromatography.

  Here, examples of the organic solvent insoluble in water include aromatic hydrocarbon solvents such as toluene, xylene, and chlorobenzene; aliphatic hydrocarbon solvents such as pentane, hexane, and heptane; halogenated hydrocarbons such as dichloromethane, dichloroethane, and chloroform. Solvents; ether solvents such as diethyl ether, methyl tert-butyl ether and tetrahydrofuran; ester solvents such as ethyl acetate;

  Examples of the aryl ethers thus obtained include 1-nitro-4-phenoxybenzene, 1-nitro-4- (phenoxyphenoxy) benzene, 4-fluoro-3-phenoxytoluene, 1-methyl-3- (4-nitro Phenoxy) benzene, 1-cyano-2-phenoxybenzene, 1-cyano-3- (4-chlorophenoxy) benzene, 1-methyl-3- (4-chlorophenoxy) benzene, 2,4-dichloro-1- ( 4-nitrophenoxy) benzene, 4-methyl-2-phenoxy-1-fluorobenzene, 2,4-dichloro-6-fluoro-1- (4-nitrophenoxy) benzene, 2-chloro-4-trifluoromethyl- 1- (4-nitrophenoxy) benzene, 3- (2-chloro-4-trifluoromethylphenoxy) tolu 4- (2-fluoro-4-cyanophenoxy) anisole, 4-phenylthionitrobenzene, 2-phenoxypyridine, 4-phenoxypyridine, 2- (4-chlorophenoxy) pyridine, 3-trifluoromethyl-2- (3-methylphenoxy) pyridine, 3-fluoro-5-chloro-2- (4-methoxyphenoxy) pyridine, 3-chloro-5-trifluoromethyl-2- (4-methoxyphenoxy) pyridine, 3-nitro- 2- (3-chlorophenoxy) pyridine, 6-bromo-2- (3-methylphenoxy) pyridine, 2,6-bis (3-methylphenoxy) pyridine, 8-chloro-4- (2-chloro-4- Fluorophenoxy) quinoline, 2-chloro-4- [4- (4-hydroxyphenoxy) phenoxy] pyridine, Examples include diphenyl ether, 4-chlorophenyl benzyl ether, 4-methylphenyl benzyl ether, 4-chlorobenzyl phenyl ether, anisole, ethyl phenyl ether, 3-methylphenyl propyl ether, isopropyl phenyl ether, cyclohexyl phenyl ether, octyl phenyl ether, and the like. It is done.

After the reaction, the substituent undergo nucleophilic substitution reactions Y ^- as imidazolium salts containing as can be recovered alkyl substituted imidazolium cations. The imidazolium salt recovered from the reaction solution by filtration, separation, or the like is ion-exchanged using, for example, silver fluoride or potassium fluoride as necessary, and a part or all of Y ⁻ is fluoride. By making it into ions, it can be reused as the imidazolium salt (1). When the collected imidazolium salt contains fluoride ions, it may be reused as the imidazolium salt (1) without ion exchange. Of course, when the substituent that undergoes the nucleophilic substitution reaction is a fluorine atom, the recovered imidazolium salt (1) may be reused as it is.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by these Examples.

Experimental Example 1 (Production example of imidazolium salt (1) where x = 1)
In a triangular flask, 22 g of 1-methyl-3- (n-butyl) imidazolium chloride and 200 g of water were charged and dissolved. In another triangular flask, 16.1 g of silver (I) fluoride and 120 g of water were charged and dissolved, the two aqueous solutions were mixed at 25 ° C., and stirring was continued at the same temperature for 30 minutes. Crystals precipitated after the reaction were filtered, and the crystals were washed with water. The obtained filtrate and washings were combined and concentrated to obtain 24.5 g of colorless oil. The oil crystallized on standing at room temperature. As a result of elemental analysis, the obtained crystal was identified as 1-methyl-3-n-butylimidazolium fluoride dihydrate. Yield: 100%.

Elemental analysis values: C: 49.5, H: 9.9, N: 14.5, F: 9.2
Calculated values: C: 49.5, H: 9.9, N: 14.4, F: 9.8
1H-NMR (δ ppm, DMSO-d6, TMS standard): 0.90 (t, 3H), 1.25 (m, 2H), 1.72 (m, 2H), 3.88 (s, 3H), 4.19 (t, 2H), 7.79 (d, 2H), 10.1 (bs, 1H)

Experimental Example 2 (Production example of imidazolium salt (1) where 0 <x <1)
In a triangular flask, 5.0 g of 1-methyl-3- (n-butyl) imidazolium chloride and 50 g of water were charged and dissolved. In another triangular flask, 1.72 g of silver (I) fluoride and 30 g of water were charged and dissolved, and then the two aqueous solutions were mixed at 25 ° C. and stirred at the same temperature for 30 minutes. Crystals precipitated after the reaction were filtered, and the crystals were washed with water. The obtained filtrate and washings were combined and concentrated to obtain 5.8 g of colorless oil. This oil was liquid even at 0 ° C. As a result of elemental analysis, the obtained oil was a 2 water salt of a salt composed of a mixed anion of fluoride ion 47.5 mol% and chloride ion 52.5 mol% and 1-methyl-3-n-butylimidazolium cation. Identified as Japanese.
Yield: 100%.

Elemental analysis values: C: 48.2, H: 9.5, N: 14.1, F: 4.6, Cl: 9.5
Calculated values: C: 47.4, H: 9.5, N: 13.8, F: 4.5, Cl: 9.2
1H-NMR (δ ppm, DMSO-d6, TMS standard): 0.88 (t, 3H), 1.25 (m, 2H), 1.78 (m, 2H), 3.90 (s, 3H), 4.19 (t, 2H), 7.85 (d, 2H), 10.0 (bs, 1H)

Example 1
A 50 mL flask equipped with a reflux condenser was charged with 140 mg of m-cresol, 600 mg of the imidazolium salt (1) synthesized in Experimental Example 2 and 2 g of dimethylacetamide and mixed, and then 183 mg of 3-nitro-4-chlorobenzonitrile was added. The mixture was stirred and stirred at 100 ° C. for 4 hours. After cooling to room temperature, 10 g of ethyl acetate and 5 g of water were added and stirred and allowed to stand to separate into two layers. The upper layer was washed twice with 5 g of 5% aqueous sodium hydroxide and then concentrated to obtain 242 mg of pale yellow crystals. This product was identified as 1-methyl-3- (2-nitro-4-cyanophenoxy) benzene by GC-MS and NMR analysis, and analyzed by gas chromatography (area percentage method). As a result, the purity was 100. %Met.
Yield: 95% (based on 3-nitro-4-chlorobenzonitrile)
GC-MS: M + = 254
1H-NMR (δ ppm, DMSO-d6, TMS standard): 2.40 (s, 3H), 6.8-7.2 (m, 4H), 7.25 (d, 1H), 7.72 (d 1H), 8.22 (s, 1H)

Example 2
A 50 mL flask equipped with a reflux condenser was charged with 144 mg of 2-naphthol, 300 mg of the imidazolium salt (1) synthesized in Experimental Example 1 and 2 g of dimethylacetamide, mixed, and then charged with 158 mg of 4-nitrochlorobenzene at 100 ° C. Stir for 4 hours. After cooling to room temperature, 10 g of ethyl acetate and 5 g of water were added and stirred and allowed to stand to separate into two layers. When the upper layer containing 2- (4-nitrophenoxy) naphthalene was analyzed by gas chromatography (internal standard method), the yield of 2- (4-nitrophenoxy) naphthalene was 85% (4 -Based on nitrochlorobenzene).

Example 3
A 50 mL flask equipped with a reflux condenser was charged with 120 mg of m-cresol, 30 mg of the imidazolium salt (1) synthesized in Experimental Example 1, 200 mg of potassium carbonate and 2 g of dimethylacetamide, and after mixing, 158 mg of 4-nitrochlorobenzene was charged. , And stirred at 100 ° C. for 4 hours. After cooling to room temperature, 10 g of ethyl acetate and 5 g of water were added and stirred and allowed to stand to separate into two layers. When the upper layer containing 3-methyl- (4-nitrophenoxy) benzene was analyzed by gas chromatography (internal standard method), the yield of 3-methyl- (4-nitrophenoxy) benzene was 91%. (Based on 4-nitrochlorobenzene).

Comparative Example The same procedure as in Example 3 was performed except that the imidazolium salt (1) synthesized in Experimental Example 1 was not used. The yield of 3-methyl- (4-nitrophenoxy) benzene was 68% (based on 4-nitrochlorobenzene).

Example 4
A 50 mL flask equipped with a reflux condenser was charged with 130 mg of m-cresol, 300 mg of the imidazolium salt (1) synthesized in Experimental Example 1 and 2 g of dimethylacetamide, mixed, and then 182 mg of 3-trifluoromethyl-2-chloropyridine. And stirred at 100 ° C. for 4 hours. After cooling to room temperature, 10 g of ethyl acetate and 5 g of water were added and stirred and allowed to stand to separate into two layers. The upper layer was washed twice with 5 g of 5% aqueous sodium hydroxide and then concentrated to obtain 209 mg of a yellow oil. This product was identified as 3-trifluoromethyl-2- (3-methylphenoxy) pyridine by GC-MS and analyzed by gas chromatography (area percentage method). As a result, the purity was 58%.
Yield: 48% (based on 3-trifluoromethyl-2-chloropyridine)
GC-MS: M + = 253

Example 5
A 50 mL flask equipped with a reflux condenser was charged with 240 mg of m-cresol, 40 mg of the imidazolium salt (1) synthesized in Experimental Example 1, 400 mg of potassium carbonate and 3 g of dimethylacetamide, and after mixing, 237 mg of 2,6-dibromopyridine. And stirred at 120 ° C. for 4 hours. After cooling to room temperature, 10 g of ethyl acetate and 5 g of water were added and stirred and allowed to stand to separate into two layers. The upper layer was analyzed by gas chromatography (internal standard method). The yield of 6-bromo-2- (3-methylphenoxy) pyridine was 51% and 2,6-bis (3-methylphenoxy) pyridine. Was 45% (based on 2,6-dibromopyridine).

Example 6
A 50 mL flask equipped with a reflux condenser was charged with 120 mg of thiophenol, 240 mg of the imidazolium salt (1) synthesized in Experimental Example 1 and 2 g of diethylene glycol dimethyl ether, mixed, and then charged with 158 mg of 4-nitrochlorobenzene at 4 ° C. at 4 ° C. Stir for hours. After cooling to room temperature, 10 g of ethyl acetate and 5 g of water were added and stirred and allowed to stand to separate into two layers. When the upper layer containing 4-phenylthionitrobenzene was analyzed by gas chromatography (internal standard method), the yield of 4-phenylthionitrobenzene was 91% (based on 4-nitrochlorobenzene).

Example 7
A 50 mL flask equipped with a reflux condenser was charged with 202 mg of 4,4′-dihydroxydiphenyl ether, 300 mg of the imidazolium salt (1) synthesized in Experimental Example 1, and 155 mg of 4-nitro-2-chloropyridine, and then at 80 ° C. for 5 hours. Stir. After cooling to room temperature, 10 g of ethyl acetate and 5 g of water were added and stirred and allowed to stand to separate into two layers. The organic layer was concentrated to give 340 mg of a yellow solid. This product was identified as 2-chloro-4- [4- (4-hydroxyphenoxy) phenoxy] pyridine by GC-MS and analyzed by gas chromatography (area percentage method). As a result, the purity was 60%. It was.
Yield: 65% (based on 4-nitro-2-chloropyridine)
GC-MS: M + = 313

Example 8
A 50 mL flask equipped with a reflux condenser was charged with 188 mg of phenol, 400 mg of the imidazolium salt (1) synthesized in Experimental Example 1, and 253 mg of benzyl chloride, and stirred at 100 ° C. for 4 hours. After cooling to room temperature, 10 g of ethyl acetate and 5 g of water were added and stirred and allowed to stand to separate into two layers. When the upper layer containing benzyl phenyl ether was analyzed by gas chromatography (internal standard method), the yield of benzyl phenyl ether was 75% (based on phenol).

Example 9
A 50 mL flask equipped with a reflux condenser was charged with 188 mg of phenol, 400 mg of the imidazolium salt (1) synthesized in Experimental Example 1, and 386 mg of 1-octyl bromide, and stirred at 100 ° C. for 4 hours. After cooling to room temperature, 10 g of ethyl acetate and 5 g of water were added and stirred and allowed to stand to separate into two layers. When the upper layer containing octylphenyl ether was analyzed by gas chromatography (internal standard method), the yield of octylphenyl ether was 62% (phenol basis).

Claims (7)

Formula (1)

(Wherein R ¹ and R ³ are the same or different and each represents a substituted or unsubstituted alkyl group; R ² , R ⁴ and R ⁵ are the same or different and each represents a hydrogen atom or substituted or unsubstituted; .Y to represent a substituted alkyl group ^- represents a monovalent anion other than a fluoride ion also is a 0 <x ≦ 1)..
Aryl ethers characterized in that an organic compound having one or more substituents undergoing a nucleophilic substitution reaction and a phenol are allowed to act in the presence of an alkyl-substituted imidazolium salt containing a fluoride ion represented by Manufacturing method. Y ^- 1 monovalent anion represented by is a halide ions, borate ions, ions phosphoric acid process according to claim 1 antimonate ions, sulfonic acid ions or amide ions. An organic compound having one or more substituents that undergo a nucleophilic substitution reaction has the formula (2)

(In the formula, R represents a substituted or unsubstituted aryl group or a substituted or unsubstituted alkyl group; Z represents a halogen atom, a nitro group, a sulfo group, a substituted or unsubstituted alkylsulfonyloxy group, a substituted or unsubstituted group; Represents an arylsulfonyloxy group, a substituted or unsubstituted alkylcarbonyloxy group or a substituted or unsubstituted arylcarbonyloxy group.)
A compound represented by
Phenols are represented by the formula (3)

(In the formula, Ar represents a substituted or unsubstituted aryl group, and Q represents an oxygen atom or a sulfur atom.)
A compound represented by
Aryl ethers can be represented by the formula (4)

(In the formula, R, Q and Ar each have the same meaning as described above.)
The manufacturing method of Claim 1 which is a compound shown by these. The production method according to claim 3, wherein R in Formula (2) is a substituted or unsubstituted aryl group. The production method according to claim 1, which is carried out in the presence of an inorganic base. 6. The method according to claim 5, wherein the inorganic base is an alkali metal carbonate or an alkaline earth metal carbonate. 2. The production method according to claim 1, wherein the alkyl-substituted imidazolium salt containing the fluoride ion represented by the formula (1) is recovered after the production of the aryl ether, and the alkyl-substituted imidazolium salt containing the fluoride ion is recovered. How to use recycle.