JP2009079005A - Method for producing alkylphenol derivative - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing an alkylphenol derivative. <P>SOLUTION: The method for producing an alkylphenol derivative represented by the formula (4) etc., comprises reacting a phenol compound with a hydroxy compound in the presence of a compound of a Group 4 to 10 element of the periodic table and a base. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for producing an alkylphenol derivative useful as a raw material for phenol resins, synthetic dyes, plasticizers, medicines, agricultural chemicals and the like.

  Conventionally, it is known to produce an alkylphenol derivative by reacting a phenol compound with a hydroxy compound in the presence of a strong alkali (see Patent Documents 1 to 3). However, in either case, a large amount of base is used, a high temperature and a high pressure condition of 200 ° C. or higher are required, the reaction yield is low, a large amount of by-products are by-produced, and the material of the reactor is There were problems such as being restricted. That is, the present condition is that the method of manufacturing an alkylphenol derivative with a high yield on mild conditions is not established.

Japanese Patent Laid-Open No. 6-41009 JP 56-71030 A U.S. Pat. No. 2,841,623

  Accordingly, an object of the present invention is to provide a method capable of efficiently producing an alkylphenol derivative having a substituent such as an alkyl group or an alkoxy group on an aromatic hydrocarbon ring under mild conditions.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors greatly reduce the amount of base used when a phenol compound and a hydroxy compound are reacted in the presence of a group 4-10 element compound in the periodic table. The present invention has been completed by finding that an alkylphenol derivative can be produced in a high yield under mild conditions of normal pressure and reaction temperature of less than 150 ° C.

（式中、Ａｒは単環又は多環の芳香族炭化水素基、Ｒ¹はＡｒに結合している置換基であって有機基を示す。ｎは０〜４の整数を示す）
で表されるフェノール化合物と、下記式（２）

（式中、Ｒ²、Ｒ³は、同一又は異なって、水素原子又は有機基を示す。Ｒ²、Ｒ³は、互いに結合して隣接する原子と共に非芳香族性の環を形成していてもよい）
で表されるヒドロキシ化合物とを反応させて、下記式（３）

（式中、Ａｒ、Ｒ¹、Ｒ²、Ｒ³、ｎは前記に同じ）
及び／又は、下記式（４）

（式中、Ａｒ、Ｒ¹、Ｒ²、Ｒ³、ｎは前記に同じ）
で表されるアルキルフェノール誘導体を得ることを特徴とするアルキルフェノール誘導体の製造方法を提供する。 That is, the present invention provides the following formula (1) in the presence of a periodic table group 4-10 element compound and a base.

(In the formula, Ar represents a monocyclic or polycyclic aromatic hydrocarbon group, R ¹ represents a substituent bonded to Ar, and represents an organic group. N represents an integer of 0 to 4)
And a phenol compound represented by the following formula (2)

(In the formula, R ² and R ³ are the same or different and each represents a hydrogen atom or an organic group. R ² and R ³ are bonded to each other to form a non-aromatic ring together with adjacent atoms. Also good)
Is reacted with a hydroxy compound represented by the following formula (3):

(In the formula, Ar, R ¹ , R ² , R ³ and n are the same as above)
And / or the following formula (4)

(In the formula, Ar, R ¹ , R ² , R ³ and n are the same as above)
A method for producing an alkylphenol derivative, characterized in that an alkylphenol derivative represented by the formula:

  In the method for producing an alkylphenol derivative of the present invention, various alkylphenol derivatives can be efficiently produced from a phenol compound and a hydroxy compound under mild conditions. In addition, the number of bases used can be greatly reduced, and the labor required for the treatment of the waste liquid discharged after the production of the alkylphenol derivative can be reduced. Moreover, since the production | generation of the by-product caused by a large amount of bases can be suppressed, the yield of the target product can be improved.

[Phenol Compound Represented by Formula (1)]
The phenol compound used as a raw material in the present invention is represented by the above formula (1). In formula (1), Ar represents a monocyclic or polycyclic aromatic hydrocarbon group, R ¹ represents an organic group, and n represents an integer of 0 to 4.

  Examples of the monocyclic or polycyclic aromatic hydrocarbon ring constituting the monocyclic or polycyclic aromatic hydrocarbon group in Ar include 1 to 3 such as a benzene ring, a naphthalene ring, a phenanthrene ring, an anthracene ring, and a naphthacene ring. There are about 10 aromatic hydrocarbon rings. Among these, 1 to 5 aromatic hydrocarbon rings, particularly a benzene ring and a naphthalene ring are preferable.

The organic group in R ¹ may be any group that does not inhibit this reaction (for example, a group that is non-reactive under the reaction conditions in the present method), and examples thereof include hydrocarbon groups, heterocyclic groups, substituted oxy groups. Carbonyl group (alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, cycloalkyloxycarbonyl group, etc.), carboxyl group, substituted or unsubstituted carbamoyl group, cyano group, acyl group (acetyl group, propionyl group, etc. aliphatic) An acyl group; an acetoacetyl group; an aromatic acyl group such as a benzoyl group), a substituted oxy group, a substituted thio group, a mono- or di-substituted amino group, and a group in which two or more of these are bonded. The carboxyl group or the like may be protected with a protective group known or commonly used in the field of organic synthesis, and may be substituted with a metal. The hydrocarbon group and the heterocyclic group also include a hydrocarbon group and a heterocyclic group having a substituent.

The hydrocarbon group for R ¹ includes an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and a group in which these are bonded. Examples of the aliphatic hydrocarbon group include 1 to 20 carbon atoms (preferably 1 to 1) such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, hexyl, decyl, and dodecyl groups. 10, more preferably an alkyl group of about 1 to 3); an alkenyl group of about 2 to 20 carbon atoms (preferably 2 to 10, more preferably 2 to 3) such as vinyl, allyl, 1-butenyl group; Examples thereof include alkynyl groups having about 2 to 20 carbon atoms (preferably 2 to 10, more preferably 2 to 3) such as propynyl groups.

Examples of the alicyclic hydrocarbon group include a cycloalkyl group having about 3 to 20 members (preferably 3 to 15 members, more preferably 5 to 8 members) such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl groups; Cycloalkenyl groups of about 3 to 20 members (preferably 3 to 15 members, more preferably 5 to 8 members) such as cyclopentenyl and cyclohexenyl groups; perhydronaphthalen-1-yl group, norbornyl, adamantyl, tetracyclo [ 4.4.0.1 ^2,5 . 1 ^7,10 ] bridged cyclic hydrocarbon groups such as dodecan-3-yl groups. Examples of the aromatic hydrocarbon group include aromatic hydrocarbon groups having about 6 to 14 (preferably 6 to 10) carbon atoms such as phenyl and naphthyl groups.

The hydrocarbon group in which an aliphatic hydrocarbon group and an alicyclic hydrocarbon group are bonded includes a cycloalkyl-alkyl group such as cyclopentylmethyl, cyclohexylmethyl, 2-cyclohexylethyl group (for example, C _3-20 cycloalkyl- C _1-4 alkyl group and the like). The hydrocarbon group in which an aliphatic hydrocarbon group and an aromatic hydrocarbon group are bonded to each other includes an aralkyl group (for example, a C _7-18 aralkyl group) and an alkyl-substituted aryl group (for example, about 1 to about 4). A phenyl group substituted with a C _1-4 alkyl group or a naphthyl group).

Preferred hydrocarbon groups include C _1-10 alkyl groups, C _2-10 alkenyl groups, C _2-10 alkynyl groups, C _3-15 cycloalkyl groups, C _6-14 aromatic hydrocarbon groups, C _3-15 A cycloalkyl-C _1-4 alkyl group, a C _7-14 aralkyl group and the like are included.

  The hydrocarbon group includes various substituents such as halogen atoms, oxo groups, hydroxyl groups, substituted oxy groups (for example, alkoxy groups, aryloxy groups, aralkyloxy groups, acyloxy groups, etc.), carboxyl groups, substituted oxycarbonyls. Groups (alkoxycarbonyl groups, aryloxycarbonyl groups, aralkyloxycarbonyl groups, etc.), substituted or unsubstituted carbamoyl groups, cyano groups, nitro groups, acyl groups, substituted or unsubstituted amino groups, sulfo groups, heterocyclic groups, etc. You may have. The hydroxyl group and carboxyl group may be protected with a protective group commonly used in the field of organic synthesis. In addition, an aromatic or non-aromatic heterocycle may be condensed with the ring of the alicyclic hydrocarbon group or aromatic hydrocarbon group.

The heterocyclic ring constituting the heterocyclic group for R ¹ includes an aromatic heterocyclic ring and a non-aromatic heterocyclic ring. Examples of such a heterocyclic ring include a heterocyclic ring containing an oxygen atom as a hetero atom (for example, 5-membered ring such as furan, tetrahydrofuran, oxazole, isoxazole, and γ-butyrolactone ring, 4-oxo-4H-pyran, tetrahydro 6-membered ring such as pyran, morpholine ring, condensed ring such as benzofuran, isobenzofuran, 4-oxo-4H-chromene, chroman, isochroman ring, 3-oxatricyclo [4.3.1.1 ^4,8 ] undecane 2-one ring, a bridged ring such as 3-oxatricyclo [4.2.1.0 ^4,8 ] nonan-2-one ring), a heterocycle containing a sulfur atom as a hetero atom (for example, thiophene, 5-membered ring such as thiazole, isothiazole, thiadiazole ring, 6-membered ring such as 4-oxo-4H-thiopyran ring, benzothiophene ring Any fused ring), heterocycles containing nitrogen atoms as heteroatoms (eg, 5-membered rings such as pyrrole, pyrrolidine, pyrazole, imidazole, triazole rings, 6-membered rings such as pyridine, pyridazine, pyrimidine, pyrazine, piperidine, piperazine rings) Ring, indole, indoline, quinoline, acridine, naphthyridine, quinazoline, a condensed ring such as a purine ring, etc.). In addition to the substituents that the hydrocarbon group may have, the heterocyclic group includes an alkyl group (eg, a C _1-4 alkyl group such as a methyl or ethyl group), a cycloalkyl group, an aryl group It may have a substituent such as (for example, phenyl, naphthyl group).

Examples of the substituted oxy group for R ¹ include ¹ to 20 carbon atoms such as methoxy, ethoxy, isopropoxy, butoxy, t-butoxy, hexyloxy, octyloxy, decyloxy, dodecyloxy, tetradecyloxy, and octadecyloxy groups. Preferably 1-12, more preferably about 1-6 alkoxy groups; 1-20 carbon atoms such as formyloxy, acetyloxy, propionyloxy, benzoyloxy groups (preferably 1-12, more preferably 1-6) A degree of acyloxy group; sulfonyloxy groups such as benzenesulfonyloxy and p-toluenesulfonyloxy groups; 2 to 21 carbon atoms such as methoxycarbonyloxy, ethoxycarbonyloxy and phenoxycarbonyloxy groups (preferably 2 to 13, more preferably 2 to 7) substituted oxycarbonyloxy groups (alkoxycarbonyloxy group, aryloxycarbonyloxy group etc.); vinyloxy, allyloxy, 1-butenyloxy and the like 1 to 20 carbon atoms (preferably 1 to 12, more preferably 1) An alkenyloxy group such as phenoxy group, 1-naphthoxy group and 2-naphthoxy group; aralkyloxy groups such as benzyloxy group; cycloalkyloxy groups such as cyclohexyloxy group and the like.

Examples of the substituted thio group in R ¹ include alkylthio groups having 1 to 20 carbon atoms (preferably about 1 to 12, more preferably about 1 to 6) such as methylthio, ethylthio, butylthio, and decylthio groups.

Examples of the mono- or di-substituted amino group in R ¹ include mono- or dialkylamino groups such as methylamino, dimethylamino, ethylamino, and diethylamino groups; cyclic amino groups such as 1-pyrrolidinyl, piperidino, and morpholino groups; acetylamino, propionylamino And acylamino groups such as benzoylamino group; and sulfonylamino groups such as benzenesulfonylamino and p-toluenesulfonylamino groups.

Preferred R ¹ is a hydrocarbon group (for example, a C _1-10 alkyl group, a C _2-10 alkenyl group, a C _2-10 alkynyl group, a C _3-15 cycloalkyl group, a C _6-14 aromatic hydrocarbon group). C _3-12 cycloalkyl-C _1-4 alkyl group, C _7-14 aralkyl group, etc.).

When R ¹ is a plurality, the plurality of R ¹ may be the same or may be different. Further, they may be bonded to each other to form a ring together with carbon atoms on the ring Ar. A ring formed by bonding a plurality of R ¹ together with the carbon atom on the ring Ar includes a 3- to 8-membered cycloalkane ring such as a cyclopropane ring, a cyclopentane ring or a cyclohexane ring; an oxetane ring, an oxolane ring, Oxane ring, dioxolane ring, dioxane ring and the like can be mentioned. These rings may have a substituent. Examples of the substituent include alkyl groups such as methyl and ethyl groups (for example, alkyl groups having 1 to 6 carbon atoms); alkoxy groups such as methoxy and ethoxy groups; halogen atoms such as fluorine, chlorine and bromine atoms. It is done.

The position at which R ¹ is bonded to Ar is not particularly limited, but from the viewpoint of reactivity, etc., other than the para position at the position to which the hydroxyl group is bonded (the position corresponding to them when ring Ar is polycyclic) It is preferable to be located at. The number n of R ¹ is an integer from 0 to 4, and among these, n is preferably 1 or 2.

  As typical phenol compounds represented by the formula (1), for example, phenol, o-cresol, m-cresol, p-cresol, 2,6-di-t-butylphenol, α-naphthol, β-naphthol, Examples include hydroquinone, resorcinol, catechol, 1-hydroxynaphthalene, 2-hydroxypyridine, 3-hydroxypyridine, 4-hydroxypyridine, 3-hydroxyfuran, and 3-hydroxythiophene. The phenol compound represented by the above formula (1) may have various substituents as long as the reaction is not inhibited.

[Hydroxy Compound Represented by Formula (2)]
The hydroxy compound used as a raw material in the present invention is represented by the above formula (2). In formula (2), R ² and R ³ are the same or different and represent a hydrogen atom or an organic group, and R ² and R ³ are bonded to each other to form a non-aromatic ring together with adjacent atoms. It may be formed. For R ^2, R ^3, examples of the organic group may be an organic group which does not inhibit the reaction (e.g., non-reactive organic groups under the reaction conditions in the process), for example, organic in the R ¹ Examples similar to the groups are given. Preferred organic groups include hydroxyl groups, substituted oxy groups (alkoxy groups, aryloxy groups, etc.) and the like.

  Hydroxy compounds include alcohol compounds such as primary alcohols and secondary alcohols. The hydroxy compound may have a plurality of hydroxyl groups, and may be any of monohydric alcohol, dihydric alcohol, polyhydric alcohol and the like. In the present invention, a tertiary alcohol is not preferable from the viewpoint of reactivity.

  Typical primary alcohols include, for example, methanol, ethanol, 1-propanol, 1-butanol, 2-methyl-1-propanol, 1-hexanol, 1-octanol, 1-decanol, 1-hexadecanol, 1 to 30 carbon atoms (preferably 1 to 20, more preferably 1 to 20) such as 2-buten-1-ol, ethylene glycol, 1,3-propanediol (trimethylene glycol), glycerin, hexamethylene glycol, pentaerythritol 15) about saturated or unsaturated aliphatic primary alcohols; saturated or unsaturated alicyclic primary alcohols such as cyclohexylmethyl alcohol and 2-cyclohexylethyl alcohol; benzyl alcohol, 2-phenylethyl alcohol and cinnamon alcohol Aromatic primary al Lumpur; and 2-hydroxy-heterocyclic primary alcohols such as methyl pyridine. Examples of the primary alcohol having a substituent at the hydrocarbon site include glycolic acid esters such as methyl glycolate and ethyl glycolate; alkylene glycol monoalkyl ethers such as 2-methoxyethanol (ethylene glycol monomethyl ether); 2 -Alkylene glycol monoaryl ethers such as phenoxyethanol (ethylene glycol monophenyl ether); dialkylene glycol monoalkyl ethers such as diethylene glycol monomethyl ether; alkylene glycol monoesters such as ethylene glycol monoacetate.

Typical secondary alcohols include, for example, 2-propanol, sec-butyl alcohol, 2-pentanol, 3-pentanol, 3,3-dimethyl-2-butanol, 2-octanol, 4-decanol, 2 -C3-C30 (preferably vicinal diols such as hexadecanol, 2-penten-4-ol, glycerin, 1,2-propanediol, 2,3-butanediol and 2,3-pentanediol (preferably 3-20, more preferably 3-15) saturated or unsaturated aliphatic secondary alcohols; 1-cyclopentylethanol, 1-cyclohexylethanol, and the like, an aliphatic hydrocarbon group to a carbon atom to which a hydroxyl group is bonded. A secondary alcohol in which an alicyclic hydrocarbon group (such as a cycloalkyl group) is bonded; cyclobutanol, Clopentanol, cyclohexanol, cyclooctanol, cyclododecanol, 2-cyclohepten-1-ol, 2-cyclohexen-1-ol, 2-adamantanol, 2-adamantanol having an oxo group in the adamantane ring, 2-hydroxy Norbornane, 3-hydroxytetracyclo [4.4.0.1 ^2,5 . 1 ^{7, 10} ] dodecane and other saturated or unsaturated alicyclic secondary alcohols (bridged) of about 3 to 20 members (preferably 3 to 15 members, more preferably 5 to 15 members, especially 5 to 8 members) Cyclic secondary alcohols); aromatic secondary alcohols such as 1-phenylethanol, 1-phenylpropanol, 1-phenylmethylethanol, diphenylmethanol; heterocyclics such as 1- (2-pyridyl) ethanol Secondary alcohol is exemplified.

As the hydroxy compound according to the present invention, in the above formula (2), R ² represents a hydrogen atom, R ³ represents an alkyl group, or a hydroxyalkyl group, a substituted oxy group-substituted alkyl group, and a primary class. A monovalent or dihydric alcohol having at least one hydroxyl moiety is preferred, and R ³ represents — (R ⁴ —O) m—R ⁵ (R ⁴ represents an alkylene group, and R ⁵ represents a hydrogen atom or a hydrocarbon group. The monovalent or dihydric alcohol represented by m is particularly preferable.

Examples of the alkylene group in R ⁴ include alkylene groups having about 1 to 12 carbon atoms such as a methylene group, an ethylene group, a methylethylene group, and a propylene group. Examples of the hydrocarbon group in R ⁵ include methyl A hydrocarbon group having about 1 to 12 carbon atoms such as a group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a methylethyl group, and a phenyl group. m represents an integer of 1 or more. Among them, an integer of 1 to 3, particularly 1, is preferable.

  As usage-amount of the hydroxy compound based on this invention, it is about 1-10 mol with respect to 1 mol of phenolic compounds used as a raw material, for example.

[Periodic Table 4-10 element compound]
In this invention, the periodic table group 4-10 element compound (a metal simple substance is included) is used as a catalyst. The periodic table group 4 element (metal) includes titanium, zirconium, and hafnium. The periodic table group 5 element (metal) includes vanadium, niobium, and tantalum. The periodic table group 6 element (metal) includes chromium, molybdenum, and tungsten. The Group 7 element (metal) of the periodic table includes manganese, technetium, and rhenium. The periodic table group 8 element (metal) includes iron, ruthenium, and osmium. The periodic table group 9 element (metal) includes cobalt, rhodium, and iridium. In addition, the Group 10 element (metal) of the periodic table includes nickel, palladium, and platinum. Periodic table 4-10 group element compounds include a wide range of inorganic and organic compounds containing 4-10 group elements of the periodic table. Examples of the inorganic compounds include simple metals, oxides, sulfides, hydroxides, halides, sulfates, oxo acids containing 4 to 10 group elements of the periodic table, or salts thereof, and inorganic complexes. Examples of the organic compound include cyanide, organic acid salt (such as acetate), and organic complex. Among these, organic compounds such as organic complexes are preferable. The ligand of the complex includes a known ligand. The valence of the group 4-10 element in the group 4-10 element compound of the periodic table is about 0-6, preferably 0-3. In particular, in the case of an iridium compound, monovalent or trivalent is preferable. Periodic table 4-10 group element compounds can be used individually or in combination of 2 or more types.

  A typical example of a periodic table group 4-10 element compound is shown by taking iridium as an example. Examples of inorganic iridium compounds include metal iridium, iridium oxide, iridium sulfide, iridium hydroxide, iridium fluoride, iridium chloride, odor, and the like. Iridium iodide, iridium iodide, iridium sulfate, iridium acid or a salt thereof (for example, potassium iridate), inorganic iridium complex [for example, hexaammineiridium (III) salt, chloropentammineiridium (III) salt, etc.] Can be mentioned.

As the organic iridium compound, for example, an organic iridium complex can be used in addition to iridium cyanide. Examples of the organic iridium complex include tris (acetylacetonato) iridium, dodecacarbonyltetrairidium (0), chlorotricarbonyliridium (I), di-μ-chlorotetrakis (cyclooctene) diiridium (I) ([IrCl (Coe) ₂ ] ₂ ), di-μ-chlorotetrakis (ethylene) diiridium (I), di-μ-chlorobis (1,5-cyclooctadiene) diiridium (I) ([IrCl (cod)] ₂ ), Di-μ-chlorodichlorobis (1,2,3,4,5-pentamethylcyclopentadienyl) diiridium (III) ([Cp ^* IrCl ₂ ] ₂ ), trichlorotris (triethylphosphine) iridium ( III), pentahydridobis (trimethylphosphine) iridium (V), chlorocarbonylbis (trif Sulfonyl phosphine) iridium (I), chlorotris (triphenylphosphine) iridium _{(I) (IrCl (PPh 3} ) 3), chloroethylene bis (triphenylphosphine) iridium (I), (pentamethylcyclopentadienyl) dicarbonyl Iridium (I), bis {1,2-bis (diphenylphosphino) ethane} iridium (I) chloride, pentamethylcyclopentadienylbis (ethylene) iridium (I), carbonylmethylbis (triphenylphosphine) iridium (I), (1,5-cyclooctadiene) (diphosphine) iridium (I) halide, 1,5-cyclooctadiene (1,2-bis (diphenylphosphino) ethane) iridium (I) hexafluoroline Acid salt, (1,5-cyclooctadiene) Bis (trialkylphosphine) iridium (I) halide, bis (1,5-cyclooctadiene) iridium tetrafluoroborate ([Ir (cod) ₂ ] ⁺ BF ₄ ⁻ ), (1,5-cyclooctadiene) (Acetonitrile) iridium tetrafluoroborate and the like.

Preferred iridium compounds include iridium complexes. Among these, organic iridium complexes, in particular, unsaturated hydrocarbons such as cyclopentene, dicyclopentadiene, cyclooctene, 1,5-cyclooctadiene, ethylene, pentamethylcyclopentadiene, benzene, toluene; nitriles such as acetonitrile; Ethers such as tetrahydrofuran; organic iridium complexes having phosphines such as triphenylphosphine as a ligand [for example, di-μ-chlorotetrakis (cyclooctene) diiridium (I), di-μ-chlorotetrakis (ethylene) Diiridium (I), di-μ-chlorobis (1,5-cyclooctadiene) diiridium (I) ([IrCl (cod)] ₂ ), di-μ-hydroxybis (1,5-cyclooctadiene) Diiridium (I) ([IrOH (cod) _2), di -μ- chloro dichloro bis (1,2,3,4,5-pentamethylcyclopentadienyl) diiridium ^{(III) ([Cp * IrCl} 2] 2), bis (1,5-cyclo Octadiene) iridium tetrafluoroborate, (1,5-cyclooctadiene) (acetonitrile) iridium tetrafluoroborate, etc.] are preferred.

  Examples of Group 4-10 element compounds other than iridium compounds include compounds corresponding to the above iridium compounds [for example, dichloro (1,5-cyclooctadiene) ruthenium, dichloro (1,5-cyclooctadiene) platinum. , Dichlorobis (1,5-cyclooctadiene) dirhodium, etc.]. In transition element compounds other than iridium compounds, for example, cyclopentene, dicyclopentadiene, cyclooctene, 1,5-cyclooctadiene, ethylene, pentamethylcyclopentadiene, benzene, toluene and other unsaturated hydrocarbons; acetonitrile and other nitriles Organic complexes having ethers such as tetrahydrofuran as ligands are particularly preferred.

  As the periodic table group 4-10 element compound according to the present invention, among the periodic table group 4-10 element compound, the periodic table group 8 element and the periodic table group 9 element compound are preferable, and the platinum group element (ruthenium, rhodium). , Palladium, osmium, iridium, platinum) compounds are more preferred, and iridium compounds are particularly preferred.

  The group 4-10 element compound of the periodic table can be used as it is or in a form supported on a carrier. Examples of the carrier include conventional carriers for supporting a catalyst, for example, metal oxides such as silica, alumina, silica-alumina, zeolite, titania, and magnesia, and activated carbon. In the carrier-supported catalyst, the supported amount of the group 4-10 element compound of the periodic table is, for example, about 0.1 to 50% by weight, preferably about 1 to 20% by weight with respect to the carrier. The catalyst can be supported by a conventional method such as an impregnation method, a precipitation method, or an ion exchange method.

  Although the usage-amount of a 4-10 group element compound of a periodic table can be suitably selected according to the kind of raw material, the kind of catalyst, etc., generally with respect to 1 equivalent of phenolic compounds represented by the said Formula (1) used as a raw material. For example, 0.0001 to 1 equivalent, preferably 0.001 to 0.3 equivalent, more preferably 0.001 to 0.05 molar equivalent.

[base]
In the present invention, the phenol compound represented by the above formula (1) is reacted with the hydroxy compound represented by the above formula (2) in the presence of a base together with the 4-10 group element compounds of the periodic table. To do. The base may be any of an inorganic base, an organic base, a Lewis base and the like, and a base usually used for aldol condensation is preferable.

  Examples of the inorganic base include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, and cesium hydroxide; alkali metal carbonates such as lithium carbonate, sodium carbonate, potassium carbonate, and cesium carbonate; hydrogen carbonate Alkali metal hydrogen carbonates such as sodium, potassium hydrogen carbonate and cesium hydrogen carbonate; Alkaline earth metal hydroxides such as magnesium hydroxide, calcium hydroxide and barium hydroxide; Alkaline earth such as magnesium carbonate, calcium carbonate and barium carbonate Metal carbonates; cerium carbonate and the like.

  Examples of the organic base include alkali metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide; alkali metal organic acid salts such as sodium acetate; amines such as triethylamine, piperidine, N-methylpiperidine and pyridine ( Tertiary amines) and nitrogen-containing heterocyclic compounds.

  Among these, strong bases such as alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal alkoxides such as potassium t-butoxide are particularly preferable.

  The amount of the base added varies depending on the type of raw material, the periodic table 4-10 group element compound, and the like, but is generally 0.001 relative to 1 equivalent of the phenol compound represented by the above formula (1) used as the raw material. About 01 to 2 equivalents, preferably about 0.01 to 1.5 equivalents. According to the method for producing an alkylphenol derivative according to the present invention, the amount of the base used can be greatly reduced.

[reaction]

  In the method for producing an alkylphenol derivative according to the present invention, an alkylphenol represented by the formula (3) is reacted with a phenol compound represented by the formula (1) and a hydroxy compound represented by the formula (2). In the method for producing the derivative and / or the alkylphenol derivative represented by formula (4), it can be produced in a high yield under mild conditions by using a group 4-10 element compound of the periodic table as a catalyst. , It is characterized in that the amount of base used can be remarkably reduced as compared with the prior art.

  The reaction of the phenol compound represented by the above formula (1) and the hydroxy compound represented by the above formula (2) is carried out in the presence or absence of a solvent. The solvent may be any solvent that dissolves the phenol compound represented by the above formula (1) and the hydroxy compound represented by the above formula (2) and is inert to the reaction. Aliphatic hydrocarbons such as cyclohexane, hexane, heptane, and octane; cycloaliphatic hydrocarbons such as cyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; halogenated carbonization such as chloroform, dichloromethane, and 1,2-dichloroethane Hydrogen; ethers such as diethyl ether, dimethoxyethane, tetrahydrofuran and dioxane; amides such as N, N-dimethylformamide and N, N-dimethylacetamide. These solvents are used alone or in admixture of two or more.

  In addition, when using a primary alcohol about the hydroxy compound represented by Formula (1) used as a raw material, you may add a corresponding aldehyde to a reaction system a little. The addition of the aldehyde is preferable in that the reaction rate may be improved.

  Further, for example, phosphines such as triphenylphosphine may be added to the reaction system as a ligand. By adding a ligand, a chelate complex is formed with Group 4-10 elements of the periodic table, the catalytic activity is improved, and a phenol compound and a hydroxy compound are reacted under milder conditions to produce an alkylphenol derivative. It is preferable in that it can be performed. As addition amount of phosphines, such as a triphenylphosphine, it is about 0.001-0.1 equivalent with respect to 1 equivalent of phenolic compounds represented by the said Formula (1), for example.

  The reaction may be performed in the presence of a polymerization inhibitor. The reaction temperature can be appropriately selected according to the reaction raw material and the type of the periodic table group 4-10 element compound, and is, for example, about 20 to 200 ° C, preferably about 50 to 180 ° C, and more preferably about 50 to 150 ° C. The reaction may be carried out at normal pressure or under reduced pressure or increased pressure. The reaction atmosphere is not particularly limited as long as it does not inhibit the reaction, but it is preferable to carry out the reaction in an inert gas atmosphere such as a nitrogen atmosphere or an argon atmosphere. In the presence of a small amount of oxygen, the oxygen may function as a hydrogen acceptor and the reaction rate may be increased. However, when excess oxygen is present in the system, other reactions tend to proceed. Therefore, it is desirable that the oxygen concentration in the gas phase part of the reaction system is, for example, 10% or less, preferably 5% or less, more preferably 1% or less. The reaction can be carried out by any method such as batch, semi-batch and continuous methods. Moreover, the phenolic compound represented by the above formula (1) used as a raw material may be charged all at once, or may be charged continuously or intermittently.

  In the method of the present invention, the phenol compound represented by the above formula (1) reacts with the hydroxy compound represented by the above formula (2) to represent the above formula (3) and / or the above formula (4). To produce an alkylphenol derivative. For example, when an alcohol having a substituted oxy group is used for the hydroxy compound represented by the formula (2) used as a raw material in the reaction, the phenol compound represented by the formula (1) and the formula (2) are used. ) To produce an alkylphenol derivative represented by the above formula (3), which is further represented by the above formula (1) to the alkylphenol derivative represented by the above formula (3). A phenol compound reacts to produce an alkylphenol derivative represented by the above formula (4). On the other hand, when an alcohol having no substituted oxy group is used for the hydroxy compound represented by the formula (2) used as a raw material, the reaction is performed at the stage when the alkylphenol derivative represented by the formula (3) is generated. Often ends.

  Although the reaction mechanism is not necessarily clear, the hydroxy compound represented by the formula (2) is first oxidatively dehydrogenated by a group 4-10 element compound of the periodic table to become an aldehyde (at this time, the group 4-10 element compound of the periodic table). This is caused to undergo a condensation reaction at, for example, the para position of the phenol compound represented by the formula (1), and is further hydrogenated by the hydrogenated group 4-10 element compound of the periodic table to obtain an alkyl. It is presumed that a phenol compound (an alkylphenol derivative represented by the above formula (3)) having a group bonded thereto is generated (at this time, the original periodic table group 4-10 element compound is regenerated). Moreover, about the hydroxy compound represented by said Formula (2) used as a raw material, when the alcohol which has a substituted oxy group is used, since a substituted oxy group has the property as an electron-donating group, said formula (3). It is speculated that the alkylphenol derivative represented by formula (1) further reacts with the alkylphenol derivative represented by formula (1) to produce the alkylphenol derivative represented by formula (4).

  After completion of the reaction, the reaction product can be separated and purified by separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, etc., or a separation means combining these.

  According to the method for producing an alkylphenol derivative according to the present invention, since the group 4-10 element compound of the periodic table is used as a catalyst, the target alkylphenol derivative can be produced under mild conditions. The alkylphenol derivative thus obtained can be used as a raw material for phenol resins, synthetic dyes, plasticizers, medicines, agricultural chemicals and the like. Furthermore, the amount of base to be used can be greatly reduced as compared with the conventional case, and the labor required for processing the waste liquid discharged after production can be reduced. Moreover, since the production | generation of the by-product caused by a large amount of bases can be suppressed, the yield of the target product can be improved.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited by these Examples.

Example 1
Under a nitrogen atmosphere, 3,6-di-t-butylphenol 3 g, 1,3-propanediol 4.6 g, di-μ-chlorobis (1,5-cyclooctadiene) diiridium 0.15 g, triphenylphosphine 0. When a mixture of 08 g, 0.84 g of potassium hydroxide and 9 g of dioxane was reacted at 80 ° C. for 18 hours, 2,6-di-t-butyl-4- (3-hydroxypropyl) phenol was converted to 2, Based on 6-di-t-butylphenol, it was produced in a yield of 60%.

Example 2
When 0.03 g of di-μ-chlorobis (1,5-cyclooctadiene) diiridium was used and reacted at 105 ° C. under the same conditions as in Example 1, 2,6-di- t-Butyl-4- (3-hydroxypropyl) phenol was produced in 49% yield based on 2,6-di-t-butylphenol.

Example 3
Under a nitrogen atmosphere, 3 g of 2,6-di-t-butylphenol, 4.42 g of 2-methoxyethanol, 0.15 g of di-μ-chlorobis (1,5-cyclooctadiene) diiridium, 0.08 g of triphenylphosphine, And a mixture of sodium hydroxide 0.17 g was reacted at 120 ° C. for 14 hours, and 2,6-di-t-butyl-4- (2-methoxyethyl) phenol was converted to 2,6-di-t -Based on butylphenol, yield 52%, 2,2-bis (3,5-di-t-butyl-4-hydroxyphenyl) -1-methoxyethane based on 2,6-di-t-butylphenol As a yield of 34%.

Example 4
Under a nitrogen atmosphere, 3 g of 2,6-di-t-butylphenol, 4.42 g of 2-methoxyethanol, 0.12 g of dichloro (1,5-cyclooctadiene) ruthenium, 0.08 g of triphenylphosphine, and potassium hydroxide When 0.28 g of the mixture was reacted at 120 ° C. for 17 hours, 2,6-di-t-butyl-4- (2-methoxyethyl) phenol was based on 2,6-di-t-butylphenol. , 27% yield, 2,2-bis (3,5-di-tert-butyl-4-hydroxyphenyl) -1-methoxyethane based on 2,6-di-tert-butylphenol yield 48 %.

Example 5
A reaction was carried out under the same conditions as in Example 4 except that 0.12 g of dichloro (1,5-cyclooctadiene) palladium was used instead of dichloro (1,5-cyclooctadiene) ruthenium. 2,6-di-tert-butyl-4- (2-methoxyethyl) phenol and 2,2-bis (3,5-di-tert-butyl-4-hydroxyphenyl) -1-methoxyethane Based on 6-di-t-butylphenol, it was produced in a yield of 13%.

Example 6
The reaction was conducted under the same conditions as in Example 4 except that 0.11 g of di-μ-chlorobis (1,5-cyclooctadiene) dirhodium was used instead of dichloro (1,5-cyclooctadiene) ruthenium. Trace amounts of 2,6-di-tert-butyl-4- (2-methoxyethyl) phenol and 2,2-bis (3,5-di-tert-butyl-4-hydroxyphenyl) -1-methoxy Ethane was produced in 15% yield based on 2,6-di-t-butylphenol.

Example 7
Under a nitrogen atmosphere, 3 g of 2,6-di-t-butylphenol, 4.42 g of 2-methoxyethanol, 0.15 g of di-μ-chlorobis (1,5-cyclooctadiene) diiridium, and 0. When 95 g of the mixture was reacted at 120 ° C. for 15 hours, 2,2-bis (3,5-di-t-butyl-4-hydroxyphenyl) -1-methoxyethane was converted to 2,6-di-t. -Based on butylphenol, it was produced in a yield of 70%.

Example 8
Under a nitrogen atmosphere, 413 g of 2,6-di-t-butylphenol, 1662 g of 2-phenoxyethanol, 27.1 g of di-μ-chlorobis (1,5-cyclooctadiene) diiridium, 14.3 g of triphenylphosphine, and water When a mixture of 37.6 g of potassium oxide was reacted at 120 ° C. for 14 hours, 2,6-di-t-butyl-4- (2-phenoxyethyl) phenol was converted to 2,6-di-t-butylphenol. As a reference, the yield was 24%, and 2,2-bis (3,5-di-t-butyl-4-hydroxyphenyl) -1-phenoxyethane was collected on the basis of 2,6-di-t-butylphenol. Produced at a rate of 10%.

Example 9
Under a nitrogen atmosphere, 10 g of 2,6-di-t-butylphenol, 51.4 g of diethylene glycol monomethyl ether, 0.03 g of di-μ-chlorobis (1,5-cyclooctadiene) diiridium, 0.02 g of triphenylphosphine, and When a mixture of 0.1 g of potassium hydroxide was reacted at 120 ° C. for 5 hours, 2,6-di-t-butyl-4- (2- (2-methoxyethoxy) ethyl) phenol was converted to 2,6 -Based on di-t-butylphenol, the yield was 53%, 2,2-bis (3,5-di-t-butyl-4-hydroxyphenyl) -1- (2-methoxyethoxy) ethane was 2, Based on 6-di-t-butylphenol, it was produced in a yield of 11%.

Comparative Example 1
Under a nitrogen atmosphere, a mixture of 19.8 g of 2,6-di-t-butylphenol, 56.5 g of 1,3-propanediol and 3.25 g of potassium hydroxide was heated to reflux at 200 ° C. or higher for 5 hours. 2,6-di-t-butyl-4- (3-hydroxypropyl) phenol was not obtained at all.

  The results of the above examples and comparative examples are summarized in Tables 1 and 2.

  As is clear from Tables 1 and 2 above, in Examples 1 to 9 performed by the method for producing an alkylphenol derivative according to the present invention, in the presence of a Group 4-10 element compound of the periodic table and a small amount of the base, From the phenolic compound represented by the formula (1) and the hydroxy compound represented by the above formula (2), mild conditions for the alkylphenol derivative represented by the above formula (3) and / or (4) as the target compound are obtained. It was possible to manufacture efficiently below. On the other hand, in Comparative Example 1 in which the reaction was performed in the absence of the group 4-10 element compound of the periodic table, the target compound could not be obtained even under high temperature conditions exceeding 200 ° C.

Claims (1)

In the presence of a periodic table 4-10 group element compound and a base, the following formula (1)

(In the formula, Ar represents a monocyclic or polycyclic aromatic hydrocarbon group, R ¹ represents a substituent bonded to Ar, and represents an organic group. N represents an integer of 0 to 4)
And a phenol compound represented by the following formula (2)

(In the formula, R ² and R ³ are the same or different and each represents a hydrogen atom or an organic group. R ² and R ³ are bonded to each other to form a non-aromatic ring together with adjacent atoms. Also good)
Is reacted with a hydroxy compound represented by the following formula (3):

(In the formula, Ar, R ¹ , R ² , R ³ and n are the same as above)
And / or the following formula (4)

(In the formula, Ar, R ¹ , R ² , R ³ and n are the same as above)
A process for producing an alkylphenol derivative, characterized in that an alkylphenol derivative represented by the formula: