JP4844130B2 - Process for producing β-hydroxy ethers - Google Patents

Description

  The present invention relates to a method for producing β-hydroxy ethers.

  β-Hydroxyethers are important compounds as various chemicals such as intermediates for medical and agricultural chemicals and polymer materials (for example, PET) (see, for example, Patent Document 1).

  As a method for synthesizing β-hydroxy ethers, a method of reacting an epoxy compound with phenols is known, and is generally carried out in the presence of an acid catalyst or a base catalyst. Has a problem in that it produces a large amount of by-products and cannot be applied to compounds unstable to acids and bases (see, for example, Non-Patent Document 1). Therefore, as a synthesis method under conditions close to neutrality, for example, a method using polyethylene glycol as a catalyst (see, for example, Non-Patent Document 2), a method using cesium fluoride as a catalyst (see, for example, Non-Patent Document 3) ), A method using a fluorine salt as a catalyst in the presence of a specific solvent (for example, see Patent Document 2), and the like have been reported. However, in the method using polyethylene glycol, the yield is not sufficient, and in the method using a fluorine salt such as cesium fluoride, usable epoxy compounds are limited, or aprotic polar solvents that are difficult to recover are used. None of them were industrially satisfactory in that they were necessary.

JP-A-3-34951 Japanese Patent No. 3376896 J. et al. Am. Chem. Soc. 73, 1881 (1951) Tetrahedron, 50, 10483 (1994) Terahedron Lett. , 31, 1723 (1990)

  Therefore, the present inventor has intensively studied to develop an industrially more advantageous method for producing β-hydroxy ethers. As a result, the reaction between an epoxy compound and a phenol is carried out in the presence of an alkyl-substituted imidazolium salt. For example, the present inventors have found that β-hydroxy ethers are efficiently produced, and have reached the present invention.

（式中、Ｒ^１およびＲ^３は、それぞれ同一または相異なって、置換されていてもよいアルキル基を表し、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されていてもよいアルキル基を表す。Ｙ⁻およびＺ⁻は相異なる１価のアニオンを表す。また、０≦ｘ≦１である。）
で示されるアルキル置換イミダゾリウム塩の存在下に、エポキシ化合物とフェノール類とを反応させることを特徴とするβ−ヒドロキシ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 an optionally substituted alkyl group, and R ² , R ⁴ and R ⁵ are the same or different and are each a hydrogen atom or substituted. even if represents an alkyl group .Y ^- and Z ^- is representing different monovalent anion also is 0 ≦ x ≦ 1)..
The present invention provides a process for producing β-hydroxy ethers, characterized by reacting an epoxy compound with a phenol in the presence of an alkyl-substituted imidazolium salt represented by the formula:

  According to the present invention, a wide range of epoxy compounds can be used as a raw material, and β-hydroxy ethers can be efficiently produced without using an aprotic polar solvent that is difficult to recover. Is advantageous. In addition, the alkyl-substituted imidazolium salt of the present invention itself has the properties of an ionic liquid, so that it can be easily recovered and recycled. Further, by appropriately selecting x in the above formula (1) Since the melting point can be lowered to room temperature or lower, the reaction can be carried out under a wide range of temperature conditions, which is advantageous in terms of industrial handling and environment.

  First, the alkyl-substituted imidazolium salt 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 an optionally substituted alkyl group, and R ² , R ⁴ and R ⁵ are the same or different and are each a hydrogen atom or substituted. Represents an optionally substituted alkyl group.

  Here, examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, and an n-decyl group. , A cyclopropyl group, a 2,2-dimethylcyclopropyl group, a cyclopentyl group, a cyclohexyl group, a menthyl group, etc., a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. Examples of the substituent which may be present on the alkyl group include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, An optionally substituted alkoxy group having 1 to 20 carbon atoms such as a trifluoromethoxy group; an optionally substituted aryl having 6 to 20 carbon atoms such as a phenyl group, a 4-methylphenyl group and a 4-methoxyphenyl group; Group; aryloxy group having 6 to 20 carbon atoms such as phenoxy group, 2-methylphenoxy group, 4-methylphenoxy group, 4-methoxyphenoxy group, 3-phenoxyphenoxy group; fluorine atom; acetyl Group, an optionally substituted alkylcarbonyl group having 2 to 20 carbon atoms such as propionyl group; benzoyl group, 2 Methylbenzoyl group, 4-methylbenzoyl group, 4-methoxybenzoyl optionally substituted arylcarbonyl group having 7 to 20 carbon atoms such as a group; a carboxyl group; and the like. Specific examples of the alkyl group substituted with such a substituent include a fluoromethyl group, a trifluoromethyl group, a methoxymethyl group, an ethoxymethyl group, a methoxyethyl group, a benzyl group, a 4-fluorobenzyl group, and a 4-methylbenzyl group. Phenoxymethyl group, 2-oxopropyl group, 2-oxobutyl group, phenacyl group, 2-carboxyethyl group and the like.

Y ⁻ and Z ⁻ represent different monovalent anions, for example, halide ions such as fluoride ion, chloride ion, bromide ion and iodide ion; borate ions such as tetrafluoroborate anion; Phosphate ions such as hexafluorophosphate anion; antimonate ions such as hexafluoroantimonate anion; sulfonate ions such as trifluoromethanesulfonate anion; bicarbonate ion; carboxyl such as acetate anion and trifluoroacetate anion Acid ions; amide ions such as bis (trifluoromethanesulfonyl) amide anion; nitrate ions; and the like. From the viewpoint of the reactivity of etherification described below and ease of recovery, it is preferable that a halide ion is included as Y ⁻ or Z ⁻ , a fluoride ion is more preferable, and Y ⁻ is More preferably, it is a fluoride ion, and Z ⁻ is a halide ion excluding fluoride ions.

x represents the ratio of the monovalent anion represented by Y ⁻ to the total anion contained in the imidazolium salt (1), and can be arbitrarily selected within the range of 0 ≦ x ≦ 1.

  Examples of the alkyl-substituted imidazolium cation constituting the imidazolium salt (1) include 1,3-dimethylimidazolium cation, 1,2,3-trimethylimidazolium cation, 1,2,3,4-tetramethylimidazole. Cation, 1,2,3,4,5-pentamethylimidazolium cation, 1-methyl-3-ethylimidazolium cation, 1,2-dimethyl-3-ethylimidazolium cation, 1,3-diethylimidazolium Cation, 1-methyl-3- (n-propyl) imidazolium cation, 1-methyl-3- (n-butyl) imidazolium cation, 1,2-dimethyl-3- (n-butyl) imidazolium cation, 1 -Methyl-3- (n-pentyl) imidazolium cation, 1-methyl-3- (n (Hexyl) imidazolium cation, 1,3-dimethyl-2-ethylimidazolium cation, 1,3-dimethyl-2- (n-propyl) imidazolium cation, 1,3-dimethyl-2- (n-butyl) imidazole 1-dodecyl-2-methyl-3-dodecylimidazolium cation, 1-ethoxymethyl-3-methylimidazolium cation, 1-trifluoromethyl-3-methylimidazolium cation, 1- (n-dodecyl)- Examples include 2-methyl-3-benzylimidazolium cation.

  The imidazolium salt (1) may form a complex with a compound that is inert to the etherification reaction of the present invention, such as water or a polar solvent.

As the imidazolium salt (1), when x = 0 or x = 1 in the formula (1), a commercially available compound can be used. When the imidazolium salt (1) having the desired monovalent anion is not commercially available, it can be prepared using a conventional salt exchange method. Under the present circumstances, x in the said Formula (1) can be adjusted to arbitrary values in the range of 0 <x <= 1 according to preparation conditions. For example, an imidazolium salt (1) in which Y ⁻ is a fluoride ion is a fluoride such as silver fluoride or potassium fluoride, and x = 0 in the above formula (1) and Z ⁻ is a chloride ion. It can be produced using a method such as a salt exchange reaction with an alkyl-substituted imidazolium salt, and x in the above formula (1) is adjusted to an arbitrary value within the range of 0 <x ≦ 1 depending on the amount of fluoride used. 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 salt which is x = 1.

  Next, an etherification reaction between an epoxy compound and a phenol in the presence of the imidazolium salt (1) will be described.

（式中、Ｒ^６〜Ｒ^９はそれぞれ同一または相異なって、置換されていてもよいアルキル基、置換されていてもよいアルコキシ基、置換されていてもよいアリール基、置換されていてもよいアリールオキシ基、置換されていてもよいアルキルカルボニル基、置換されていてもよいアリールカルボニル基、置換されていてもよいアルコキシカルボニル基、置換されていてもよいアリールオキシカルボニル基、カルボキシ基、ハロゲン原子または水素原子を表す。また、Ｒ^６〜Ｒ^９のうち任意の二つが一緒になって環構造の一部を形成していてもよい。）
で示されるエポキシ化合物（以下、エポキシ化合物（２）と略記する。）が挙げられる。 The epoxy compound is not particularly limited as long as it is a compound having 1 or 2 or more epoxy groups in the molecule.

(In formula, R < ⁶ > -R < ⁹ > is the same or different, respectively, The alkyl group which may be substituted, the alkoxy group which may be substituted, the aryl group which may be substituted, and may be substituted Aryloxy group, optionally substituted alkylcarbonyl group, optionally substituted arylcarbonyl group, optionally substituted alkoxycarbonyl group, optionally substituted aryloxycarbonyl group, carboxy group, halogen atom Or represents a hydrogen atom, and any two of R ^{6 to} R ⁹ may be combined to form part of the ring structure.)
And an epoxy compound (hereinafter abbreviated as epoxy compound (2)).

  Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-decyl group, and cyclopropyl. And linear, branched or cyclic alkyl groups having 1 to 20 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 a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, and a tert-butoxy group. And an optionally substituted alkoxy group having 1 to 20 carbon atoms such as a trifluoromethoxy group; an optionally substituted 6 to 20 carbon atom such as a phenyl group, a 4-methylphenyl group and a 4-methoxyphenyl group. Aryl group; aryloxy group having 6 to 20 carbon atoms such as phenoxy group, 2-methylphenoxy group, 4-methylphenoxy group, 4-methoxyphenoxy group and 3-phenoxyphenoxy group; fluorine atom; A halogen atom such as a chlorine atom or a bromine atom; an acetyl group, a propionyl group, etc. Kill carbonyl group; arylcarbonyl group having 7 to 20 carbon atoms such as benzoyl group, 2-methylbenzoyl group, 4-methylbenzoyl group, 4-methoxybenzoyl group; methoxycarbonyl group, ethoxycarbonyl group, etc. An optionally substituted alkoxycarbonyl group having 7 to 20 carbon atoms; substitution of 7 to 20 carbon atoms such as phenoxycarbonyl group, 2-methylphenoxycarbonyl group, 4-methylphenoxycarbonyl group, 4-methoxyphenoxycarbonyl group, etc. Aryloxycarbonyl group which may be formed; carboxy group; hydroxyl group; amino group; Specific examples of the alkyl group substituted with such substituent include chloromethyl group, fluoromethyl group, trifluoromethyl group, methoxymethyl group, hydroxymethyl group, ethoxymethyl group, methoxyethyl group, methoxycarbonylmethyl group, 1 -Ethoxycarbonyl-2,2-dimethyl-3-cyclopropyl group, benzyl group, 4-chlorobenzyl group, 4-methylbenzyl group, 4-methoxybenzyl group, 3-phenoxybenzyl group and the like.

  Examples of the optionally substituted alkoxy group include those composed of the optionally substituted alkyl group and an oxygen atom. 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, n-decyloxy group, cyclopentyloxy group, cyclohexyloxy group, menthyloxy group, chloromethoxy group, fluoromethoxy group, trifluoro Examples include methoxy group, methoxymethoxy group, ethoxymethoxy group, methoxyethoxy group, benzyloxy group, 4-chlorobenzyloxy group, 4-methylbenzyloxy group, 4-methoxybenzyloxy group, 3-phenoxybenzyloxy group and the like. .

  As an aryl group, C6-C10 aryl 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 a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, A C1-C20 optionally substituted alkyl group such as trifluoromethyl group, methoxymethyl group, hydroxymethyl group, methoxycarbonylmethyl group, benzyl group; methoxy group, ethoxy group, n-propoxy group, isopropoxy An optionally substituted alkoxy group having 1 to 20 carbon atoms such as a group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, trifluoromethoxy group; phenyl group, 4-methylphenyl group, C6-C20 optionally substituted aryl group such as 4-methoxyphenyl group; phenoxy group, 2-methoxy Aryloxy groups having 6 to 20 carbon atoms such as ruphenoxy group, 4-methylphenoxy group, 4-methoxyphenoxy group and 3-phenoxyphenoxy group; halogens such as fluorine atom, chlorine atom and bromine atom Atom: C2-C20 optionally substituted alkylcarbonyl group such as acetyl group or propionyl group; C7 such as benzoyl group, 2-methylbenzoyl group, 4-methylbenzoyl group or 4-methoxybenzoyl group An arylcarbonyl group having -20 substituents; an alkyloxycarbonyl group having 7-20 carbon atoms such as a methoxycarbonyl group and an ethoxycarbonyl group; a phenoxycarbonyl group, a 2-methylphenoxycarbonyl group, 4-methylphenoxycarbonyl group, 4-methoxyphenoxycarbo Optionally substituted aryloxycarbonyl group having 7 to 20 carbon atoms, such as Le group; a carboxy group; an amino group; and the like. Specific examples of the aryl group substituted with such a substituent include 2-methylphenyl group, 4-chlorophenyl group, 4-methylphenyl group, 4-methoxyphenyl group, 3-phenoxyphenyl group and the like.

  Examples of the optionally substituted aryloxy group include those composed of the optionally substituted aryl group and an oxygen atom, such as a phenoxy group, 2-methylphenoxy group, 4-chlorophenoxy group, 4-methylphenoxy group, 4-methoxyphenoxy group, 3-phenoxyphenoxy group and the like can be mentioned.

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

  The optionally substituted alkylcarbonyl group is a substituent composed of a carbonyl group and the optionally substituted alkyl group, and the optionally substituted arylcarbonyl group is the carbonyl group and the substituted group. Each may be a substituent composed of an aryl group which may be an acetyl group, a propionyl group, a phenylacetyl group, a benzoyl group, a 2-methylbenzoyl group, a 4-methylbenzoyl group, a 4-methoxybenzoyl group, and the like. Illustrated.

  The optionally substituted alkoxycarbonyl group is a substituent composed of a carbonyl group and the optionally substituted alkoxy group, and the optionally substituted aryloxycarbonyl group is the above substituted carbonyl group. And an aryloxy group which may be substituted, each includes a methoxycarbonyl group, an ethoxycarbonyl group, a benzyloxycarbonyl group, a phenoxycarbonyl group, a 2-methylphenoxycarbonyl group, a 4-methylphenoxycarbonyl group. And 4-methoxyphenoxycarbonyl group.

  Examples of the ring structure when such substituents together form a part of the ring structure include a cyclopentane ring, a cyclohexane ring, a cyclopentene ring, a cyclohexene ring, and the like.

  Examples of such an epoxy compound include ethylene oxide, propylene oxide, 1,2-epoxybutane, 1,2-epoxypentane, 1,2-epoxyhexane, 1,2-epoxyheptane, 1,2-epoxyoctane, 1,2 -Epoxynonane, 1,2-epoxydecane, 3,3-dimethyl-1,2-epoxybutane, cyclopentylethylene oxide, cyclohexylethylene oxide, styrene oxide, 4- (tert-butyl) styrene oxide, 3-phenyl-1,2 -Epoxypropane, 4-methoxystyrene oxide, safrole oxide, 2,3-epoxybutane, 2-methyl-1,2-epoxypropane, 2-methyl-1,2-epoxybutane, 2,3-epoxypentane, 2 , 3-Epoxyhexane, 9,10- Methyl poxy-1-decanoate, 1,2-epoxy-3-methoxypropane, 1,2-epoxy-3-ethoxypropane, 1,2-epoxy-3-propoxypropane, 1,2-epoxy-3-butoxy Propane, 1,2-epoxy-3-phenoxypropane, 1-butoxy-2,3-epoxypropane,

Cyclopentene oxide, cyclohexene oxide, 4-methylcyclohexene oxide, cycloheptene oxide, cyclooctene oxide, cyclodecene oxide, cyclododecene oxide, β-methylstyrene oxide, stilbene oxide, isosafrole oxide, β-pinene oxide, norbornene oxide 2,5-dimethyl-2,3-epoxyhex-4-ene, 1-methyl-1,2-epoxycyclopentane, 1-methyl-1,2-epoxycyclohexane, 1- (tert-butyl) -1 , 2-epoxycyclohexane, 1-isopropyl-1,2-epoxycyclohexane, 2-calene oxide, 3-calene oxide, α-pinene oxide, 2,3-dimethyl-2,3-epoxybutane, and the like.

  For these, commercially available compounds may be used, for example, those synthesized from the corresponding alkene by the usual epoxidation method may be used.

（式中、Ａｒは置換されていてもよい芳香族基または置換されていてもよい複素芳香族基を表し、Ｑは酸素原子または硫黄原子を表す。）
で示されるフェノール類（以下、フェノール類（３）と略記する。）が挙げられる。 Phenols include aromatic compounds in which one or two or more hydrogen atoms on an optionally substituted aromatic compound or an optionally substituted heteroaromatic compound are substituted with —OH group or —SH group, or If it is a heteroaromatic compound, it will not specifically limit, For example, Formula (3)

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

  Examples of the aromatic compound include hydrocarbon aromatic compounds such as benzene and naphthalene, and examples of the heteroaromatic compound include heteroaromatic compounds such as pyridine and quinoline. Examples of the substituent that may be present on the aromatic compound or heteroaromatic compound include a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, and an optionally substituted group. An aryl group, an optionally substituted aryloxy group, an optionally substituted alkylcarbonyl group, an optionally substituted arylcarbonyl group, an optionally substituted alkoxycarbonyl group, an optionally substituted aryl Examples include oxycarbonyl group, carboxy group, formyl group, sulfonamido group, alkoxysulfonyl group, alkylsulfonyl group, arylsulfonyl group, cyano group, amino group, amide group, hydroxyl group, mercapto 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.

A halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted aryl group, an optionally substituted aryloxy group, an optionally substituted acyl group and substitution Examples of the optionally substituted alkoxycarbonyl group and optionally substituted aryloxycarbonyl group include the same substituents as those exemplified as R ^{6 to} R ⁹ in the epoxy compound (2).

  The alkoxysulfonyl group is a substituent composed of a sulfonyl group and the optionally substituted alkoxy group, and the alkylsulfonyl group is a substituent composed of a sulfonyl group and the optionally substituted alkyl group. However, examples of the arylsulfonyl group include a substituent composed of a sulfonyl group and the aryl group which may be substituted, and examples thereof include a methoxysulfonyl group, an ethoxysulfonyl group, a methylsulfonyl group, and a phenylsulfonyl group. Is done.

  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, 2,4,6-trichlorophenol, 2,4- Difluorophenol, 3,5-difluorophenol, 2,4,6-trifluorophenol, 2-chloro-4-fluorophenol, 4-trifluoromethylphenol, 4-trifluoromethyl-2-chlorophenol, 2-methoxy Phenol, 3-methoxyph 4-methoxyphenol, 2-ethoxyphenol, 3-ethoxyphenol, 4-ethoxyphenol, catechol, resorcinol, hydroquinone, methyl 4-hydroxybenzoate, benzyl 2,6-dihydroxybenzoate, methyl 6-acetylsalicylate, 4-phenylphenol, 4-phenoxyphenol, 3-phenoxyphenol, vanillin, thiophenol, 1-naphthol, 2-naphthol, 1-thionaphthol, 2-methylthiophenol, 4-chlorothiophenol, 2-fluorothiophenol, Examples include 2-hydroxypyridine, 4-hydroxypyridine, 3-hydroxypyridine, 4-chloro-2-hydroxypyridine, 4,6-dihydroxypyrimidine, and 4-hydroxyquinazoline. These may use commercially available compounds, or may be synthesized by any method.

  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 use amount of phenols can usually achieve the object of the present invention when used on the basis of a functional group based on the functional group desired to react on phenols with respect to the epoxy compound. Depending on the viewpoint, an excess amount of either one may be used as a solvent. The range of the preferable usage-amount of phenol is about 0.5-2 mol times with respect to an epoxy compound on the basis of the functional group which wants reaction. When one of the epoxy compounds or phenols is used excessively, the epoxy compound or phenols used excessively can be recovered and recycled by performing distillation operation, extraction operation, etc. as necessary after the reaction is completed. It is also possible.

  This reaction usually does not require an inert solvent, but may be carried out in the presence of a solvent.

  Examples of such a solvent include ether solvents such as methyl tert-butyl ether, tetrahydrofuran and diglyme; nitrile solvents such as acetonitrile and propionitrile; aromatic hydrocarbon solvents such as toluene and xylene;

  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.

  The amount of the imidazolium salt (1) is usually 0.001 mol times or more based on the epoxy compound, and the object of the present invention is achieved. There is no upper limit, but preferably 0.01 to 0.5 mol. Double the range.

  The mixing order of the reaction reagents is not particularly limited, and may be carried out by adjusting the reaction temperature after mixing all the reaction reagents. However, if necessary, phenols and imidazolium salts (in the presence of a solvent) It is preferable to add an epoxy compound to the mixture with 1) under reaction temperature conditions.

  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^６〜Ｒ^９、ＡｒおよびＱは、それぞれ前記と同一の意味を表す。）
で示されるβ−ヒドロキシエーテル類が得られる。 By this reaction, β-hydroxy ethers are obtained. For example, if an epoxy compound (2) and a phenol (3) are reacted, the formula (4)

(Wherein R ^{6 to} R ⁹ , Ar and Q each have the same meaning as described above.)
Β-hydroxy ethers represented by the formula

  After completion of the reaction, crystallization treatment, distillation treatment, or the like is performed, and if necessary, water and / or an insoluble organic solvent is added to extract, and the resulting organic layer is concentrated. -Hydroxy ethers can be isolated. The obtained β-hydroxy ethers may be further purified by ordinary purification means such as distillation and 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;

  The β-hydroxy ethers thus obtained include 2-phenoxyethanol, 2- (4-pyridinyloxy) ethanol, 1-phenoxy-2-propanol, 1- (4-phenoxyphenoxy) -2-propanol, 1- (4- Methylphenoxy) -2-propanol, 1- (3-methylphenoxy) -2-propanol, 1- (2-methylphenoxy) -2-propanol, 1- (3-phenoxyphenoxy) -2-propanol, 1- ( 4-hydroxyphenoxy) -2-propanol, 1- (2-hydroxyphenoxy) -2-propanol, 1,2-bis (2-hydroxypropoxy) benzene, 1,4-bis (2-hydroxypropoxy) benzene, 1 -(4-chlorophenoxy) -2-propanol, 1- (2-fluoro Enoxy) -2-propanol, 1- (2-naphthyloxy) -2-propanol, 1- (phenylthio) -2-propanol, 2-phenoxy-1-propanol, 4,4'-di (2-hydroxypropoxy) biphenyl 1-phenoxy-2-butanol, 1-phenoxy-2-pentanol, 1-phenoxy-2-hexanol, 1-phenoxy-2-heptanol, 1-phenoxy-2-octanol, 1-phenoxy-2-nonanol, 1-phenoxy-2-decanol, 1-phenoxy-3,3-dimethyl-2-butanol, 2-phenoxy-3,3-dimethyl-1-butanol, 2-phenoxy-1-cyclopentyl-1-ethanol, 2- Phenoxy-2-cyclopentyl-1-ethanol, 2-phenoxy-1-cyclohex Sil-1-ethanol, 2-phenoxy-2-cyclohexyl-1-ethanol, 2-phenoxy-1-phenylethanol, 2-phenoxy-2-phenylethanol, 2-phenoxy-1- (4-tert-butylphenyl) Ethanol, 2-phenoxy-2- (4-tert-butylphenyl) ethanol, 1-phenoxy-3-phenyl-2-propanol, 2-phenoxy-3-phenyl-1-propanol, 2-phenoxy-1- (4 -Methoxyphenyl) ethanol, 2-phenoxy-2- (4-methoxyphenyl) ethanol, 1-phenoxy-3- (3,4-methylenedioxyphenyl) -2-propanol, 2-phenoxy-3- (3 4-methylenedioxyphenyl) -1-propanol, 3-phenoxy-2-buta 1-fluoro-2-methyl-2-propanol, 3-phenoxy-2-methyl-2-butanol, 3-phenoxy-2-pentanol, 2-phenoxy-3-pentanol, 3-phenoxy-2 -Hexanol, 2-phenoxy-3-hexanol, methyl 10-phenoxy-9-hydroxy-1-decanoate, methyl 9-phenoxy-10-hydroxy-1-decanoate, 1-phenoxy-3-methoxy-2-propanol 1- (phenylthio) -3-methoxy-2-propanol, 1- (4-methylphenoxy) -3-methoxy-2-propanol, 1- (3-methylphenoxy) -3-ethoxy-2-propanol, 1 -(4-Chlorophenoxy) -3-propoxy-2-propanol, 1,3-diphenoxy-2-propano , 1,3-di (4-methylphenoxy) -2-propanol, 1,3-di (2-fluorophenoxy) -2-propanol,

2- (4-methylphenoxy) cyclopentanol, 2-phenoxycyclohexanol, 4-methyl-2-phenoxycyclohexanol, 2-phenoxycycloheptanol, 2-phenoxycyclooctanol, 2-phenoxycyclodecanol, 2- Phenoxycyclododecanol, 2-phenoxy-1-phenyl-1-propanol, 1-phenoxy-1-phenyl-2-propanol, 2-phenoxy-1,2-diphenylethanol, 2-hydroxy-2-phenoxymethyl-6 , 6-Dimethyl-bicyclo [3.1.1] heptane, 2-phenoxy-3-hydroxybicyclo [2.2.1] heptane, 2,5-dimethyl-2-hydroxy-3-phenoxy-4-ene, 1- (tert-butyl) -2-phenoxycyclohexa 1-isopropyl-2-phenoxycyclohexanol, 3,7,7-trimethyl-bicyclo [4.1.0] heptane-2-phenoxy-3-ol, 3,7,7-trimethyl-bicyclo [4] .1.0] Heptane-4-phenoxy-3-ol, 2,6,6-trimethyl-bicyclo [3.1.1] heptane-3-phenoxy-2-ol, 3-phenoxy-2,3-dimethyl -2-butanol and the like.

  After the reaction, the imidazolium salt (1) can be recovered. The imidazolium salt (1) recovered from the reaction solution by filtration, separation, or the like can be recycled as the imidazolium salt (1) as it is or by subjecting it to a concentration treatment if necessary. it can.

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

Reference 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)

Reference 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 990 mg of phenol and 200 mg of the imidazolium salt (1) synthesized in Reference Example 1, mixed, and then charged with 980 mg of cyclohexene oxide and stirred at 120 ° C. for 3 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 was analyzed by gas chromatography (internal standard method), the yield of 2-phenoxycyclohexanol was 98% (based on cyclohexene oxide), and the isomer ratio was trans: cis = 99.7. : 0.3.

Example 2
The lower layer separated in Example 1 was charged into a 50 mL flask, and water was distilled off. Furthermore, 990 mg of phenol and 980 mg of cyclohexene oxide were added and reacted and treated in the same manner as in Example 1. The yield of 2-phenoxycyclohexanol was 97% (based on cyclohexene oxide).

Example 3
In Example 1, the reaction and treatment were performed in the same manner as in Example 1 except that 1000 mg of 1,2-epoxyhexane was used instead of cyclohexene oxide.
The yield of 1-phenoxy-2-hexanol is 94%,
The yield of 2-phenoxy-1-hexanol is 4%
(All are based on 1,2-epoxyhexane).

Example 4
In Example 1, 1000 mg of 1,2-epoxyhexane was used in place of cyclohexene oxide, and 200 mg of commercially available imidazolium chloride was used in place of the imidazolium salt (1) synthesized in Reference Example 1. Reaction and treatment were conducted in the same manner as in 1.
The yield of 1-phenoxy-2-hexanol is 85%,
The yield of 2-phenoxy-1-hexanol is 5%
(All are based on 1,2-epoxyhexane).

Example 5
A 50 mL flask equipped with a reflux condenser was charged with 317 mg of 4-phenoxyphenol and 300 mg of the imidazolium salt (1) synthesized in Reference Example 1, mixed, and then charged with 200 mg of propylene oxide and stirred at 60 ° C. for 2 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 1- (4-phenoxyphenoxy) -2-propanol is 93%,
The yield of 2- (4-phenoxyphenoxy) -1-propanol is 7%
(Both based on 4-phenoxyphenol).

Example 6
A 50 mL flask equipped with a reflux condenser was charged with 1500 mg of catechol and 100 mg of the imidazolium salt (1) synthesized in Reference Example 1, mixed, and then charged with 950 mg of propylene oxide and stirred at 100 ° C. for 2 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 was analyzed by gas chromatography (internal standard method), the yield of 1- (2-hydroxyphenoxy) -2-propanol was 73% (catechol basis).

Example 7
In Example 1, the reaction and treatment were performed in the same manner as in Example 1 except that 1100 mg of thiophenol was used instead of 990 mg of phenol. The yield of 2-phenylthiocyclohexanol was 99% (based on cyclohexene oxide), and the isomer ratio was trans: cis = 97: 3.

Claims (5)

Formula (1)

(Wherein R ¹ and R ³ are the same or different and each represents an optionally substituted alkyl group, and R ² , R ⁴ and R ⁵ are the same or different and are each a hydrogen atom or substituted. even if represents an alkyl group .Y ^- and Z ^- is representing different monovalent anion also is 0 ≦ x ≦ 1)..
In the presence of an alkyl-substituted imidazolium salt represented, Ru by reacting an epoxy compound with a phenol beta - a method for producing a hydroxy ethers,
The epoxy compound has the formula (2)

(In formula, R < ⁶ > -R < ⁹ > is the same or different, respectively, The alkyl group which may be substituted, the alkoxy group which may be substituted, the aryl group which may be substituted, and may be substituted Aryloxy group, optionally substituted alkylcarbonyl group, optionally substituted arylcarbonyl group, optionally substituted alkoxycarbonyl group, optionally substituted aryloxycarbonyl group, carboxy group, halogen atom Or represents a hydrogen atom, and any two of R ^{6 to} R ⁹ may be combined to form part of the ring structure.)
An epoxy compound represented by
Phenols are represented by the formula (3)

(In the formula, Ar represents an optionally substituted aromatic group or an optionally substituted heteroaromatic group, and Q represents an oxygen atom or a sulfur atom.)
Phenols represented by
β-hydroxy ethers are represented by the formula (4)

(Wherein R ^{6 to} R ⁹ , Ar and Q each have the same meaning as described above.)
A method for producing a β-hydroxy ether, which is a β-hydroxy ether represented by the formula: In formula (1), the monovalent anion represented by Y ⁻ is a fluoride ion, and the monovalent anion represented by Z ⁻ is a halide ion, borate ion, or phosphate ion excluding fluoride ion. The method for producing a β-hydroxy ether according to claim 1, wherein the ion is antimonate ions, sulfonate ions, hydrogen carbonate ions, carboxylate ions, amide ions or nitrate ions. The method for producing a β-hydroxyether according to claim 2, wherein x = 1 in formula (1). The method for producing a β-hydroxy ether according to claim 2, wherein in formula (1), x = 0, and the monovalent anion represented by Z ⁻ is a halide ion excluding a fluoride ion. The method according to claim 1, wherein after the production of β-hydroxy ethers, the alkyl-substituted imidazolium salt represented by the formula (1) is recovered and the alkyl-substituted imidazolium salt is recycled.