JP2005060384A - Manufacturing method of phenol compound - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for industrially manufacturing a hydroxyphenyl ether in a good yield and preferentially manufacturing a para-substituted product by oxidizing a phenyl ether using a heterogeneous catalyst, and to provide a method for manufacturing an alkyl substituted phenol such as cresol and a substituted phenol compound such as sesamol using the same method. <P>SOLUTION: The method for manufacturing the phenol compound that is capable of manufacturing the hydroxyphenyl ether in a high yield and preferentially manufacturing the para-substituted product by oxidizing the phenyl ether with a peroxide in the presence of a ketone using a proton type β-zeolite as a heterogeneous catalyst. The alkyl substituted phenol such as a cresol and the substituted phenol compound such as sesamol can be manufactured by using the same method. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

The present invention relates to a method for producing a phenol compound by oxidizing a substituted benzene compound with a peroxide in the presence of a zeolite catalyst and a ketone.
In the phenol compound represented by the following formula (3), for example, o-methoxyphenol (guaiacol) in which R ¹ is a methoxy group, R ² is a hydrogen atom, and n = 1 is used as a raw material for pharmaceuticals and fragrances. (Non-patent document 1), p-methoxyphenol is an important compound used as an antioxidant or a raw material for pharmaceuticals (Patent document 1). In the phenol compound represented by the following formula (4), sesamol with p = 1 is an important compound as a raw material for producing pharmaceuticals such as antihypertensive agents.

(In the formula, R ¹ represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and R ² represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a halogen atom. , N is an integer of 1 to 5, m ′ is an integer of 0 to 4, n + m ′ = 5, the plurality of R ¹ and R ² may be the same or different, and p is 1 or (It is an integer of 2.)

In the reaction for producing hydroxyphenyl ether from phenyl ether in which R ¹ is an alkoxy group in the benzene compound represented by the following formula (1), the ortho-position is usually oxidized with o-hydroxyphenyl ether and the para-position is oxidized. P-hydroxyphenyl ether formed simultaneously (see, for example, Non-Patent Documents 2 to 4).

(In the formula, R ¹ represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and R ² represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a halogen atom. , N is an integer of 1 to 5, m is an integer of 1 to 5, n + m = 6, and a plurality of R ¹ and R ² may be the same or different.

The industrial usefulness of hydroxyphenyl ether varies depending on the substitution mode, but differs greatly between ortho-substituted and para-substituted products. For example, o-methoxyphenol is important as a raw material for pharmaceuticals and fragrances, and p-methoxyphenol is important as an antioxidant. (See Patent Document 1 and Non-Patent Document 1)
Therefore, when these are co-produced industrially, not only the yield but also the production ratio of ortho-substituted and para-substituted products becomes a problem. For this reason, each of the techniques for selectively obtaining an ortho-substituted product or a para-substituted product is important.
Examples of techniques for producing hydroxyphenyl ether in one step by oxidizing phenyl ether and preferentially producing a para-substituted product include the following.

  Among them, as a technique using a homogeneous catalyst, Non-Patent Document 2 describes a method for producing methoxyphenol in which anisole is oxidized with hydrogen peroxide using manganese polynitroporphyrin as a catalyst. In this method, the yield of methoxyphenol based on hydrogen peroxide is as high as 98%, and high para-position selectivity (ortho-position substitution product / para-position substitution product formation ratio (hereinafter referred to as o / p ratio)) = 0. However, it is difficult to obtain a large amount of catalyst, and it is difficult to recover and reuse the catalyst. When industrial production is considered, there is a problem.

  Non-Patent Document 3 describes a method for producing methoxyphenol from anisole using copper nitrate as a catalyst and hydrogen peroxide as an oxidizing agent. In this method, the reaction is allowed to proceed while controlling the pH with a phosphate buffer, thereby achieving a high yield of 94% as the methoxyphenol yield based on anisole, and an o / p ratio = 0.12. Although it shows position selectivity, it is difficult to recover the catalyst because it is a homogeneous reaction, and requires a very large amount of solvent. Therefore, when considering industrial production, the process such as recovery is complicated. .

  As a technique using a heterogeneous catalyst, Non-Patent Document 4 describes a method for producing methoxyphenol in which anisole is oxidized with hydrogen peroxide using TS-1 containing titanium in a lattice. In this method, the yield of methoxyphenol based on anisole is 67% and the o / p ratio = 0.35. As shown in Non-Patent Document 4, TS-1 is often problematic in its reproducibility of preparation, and the reaction yield is not sufficient.

Patent Document 2 describes a method for producing methoxyphenol by oxidation of anisole using a catalyst system in which an alkali metal salt of a protonic acid such as sulfuric acid and a phosphorus oxygen acid such as orthophosphoric acid are combined. There is no description.
Patent Document 3 describes a method for producing methoxyphenol in which US-Y zeolite is used as a proton type zeolite and anisole is oxidized in the presence of a ketone. However, there is no description about proton type β zeolite, and its catalytic performance is not described. Is unknown. Further, as a result of further trial by the inventor, the yield of methoxyphenol was 47.1% (o / p ratio = 2.86) and was insufficient. (See Comparative Example 2)

  As described above, regarding the technology for oxidizing phenyl ether to produce hydroxy phenyl ether with high para-selectivity, although a high reaction yield is achieved by a homogeneous catalyst, catalyst recovery and solvent recovery There is a problem as an industrial manufacturing method in terms of the above. The production method using a heterogeneous catalyst that can be easily separated and recovered and can be applied to a fixed bed can be said to be an industrially suitable production method, but production using the above TS-1 or US-Y zeolite. In the method, the reaction yield is low, and a production method using a more preferable heterogeneous catalyst has been demanded.

Moreover, the hydroxylation method of substituted benzene compounds, such as alkylbenzene and methylenedioxybenzene, using proton type β zeolite has not been known so far.
JP-A-9-151151 JP-A-3-128336 French Patent Application Publication No. 2693457 13901 Chemicals, Chemical Industry Daily, 2001, p. 653 Chemical Communications, 10 (2000), p. 827-828 Organic Preparations and Procedures Int. , 32 (2000), p. 373-405 Journal of Chemical Society Chemical Communications, 3 (1995), p. 349-350 Accounts of Chemical Research, 31 (8), (1998) p. 485-493 Journal of Physical Chemistry, 104 (2000), p. 2853-2859 Catalyst Preparation Chemistry, Kodansha (1980) p. 49-73 Keulemans, “Gas Chromatography”, Reinhold, New York, 1957, p. 39 Microporous and Mesoporous Materials, 40 (2000) p. 271-281

  An object of the present invention is to provide an industrial production method in which a phenyl ether is oxidized using a heterogeneous catalyst to preferentially produce a hydroxy phenyl ether in a good yield and a para-substituted product, and a similar method is provided. It is to provide a production method capable of producing an alkyl-substituted phenol such as cresol and a substituted phenol compound such as sesamol.

As a result of investigations to solve the above problems, the present inventors have used proton-type zeolite as a heterogeneous catalyst and oxidized phenyl ether with a peroxide in the presence of a ketone. The present inventors have found that hydroxyphenyl ether can be produced with high yield and a para-substituted product can be preferentially produced, and alkyl-substituted phenols such as cresol and substituted phenol compounds such as sesamol can be produced in the same manner.
That is, the present invention is as follows.

  The first invention comprises at least one selected from the group consisting of benzene compounds represented by the following formulas (1) and (2) in the presence of proton type β zeolite and ketone.

(Wherein R ¹ , R ² , n and p are as defined above, m is an integer of 1 to 5, and n + m = 6).
The present invention relates to a method for producing at least one phenol compound selected from the group consisting of phenol compounds represented by the following formulas (3) and (4), characterized by oxidation with a peroxide.

(Wherein R ¹ , R ² , n, m ′ and p are as defined above.)

  2nd invention is related with the manufacturing method of the phenolic compound of 1st invention whose peroxide is hydrogen peroxide or a ketone peroxide.

In the third invention, there is an acid point where the proton-type β zeolite has a desorption peak in the range of plus or minus 100 ° C. around 330 ° C. in the ammonia temperature programmed desorption method (NH ₃ -TPD) spectrum. In addition, the present invention relates to a method for producing a phenol compound of the first or second invention, which is a proton-type β zeolite having a strong acid point amount of 2.5 μmol / g or less that exhibits a desorption peak of 500 ° C. or higher.

  In the fourth invention, the proton type β zeolite is an alkaline earth metal, a transition metal, a group 2B metal, a group 3B metal from the third period to the sixth period, a group 4B metal from the fifth period to the sixth period, or a lanthanoid metal The present invention relates to a method for producing a phenol compound of the first or second invention, which is a supported proton type β zeolite.

  Almost all tar is obtained by oxidizing a phenyl ether with a peroxide in the presence of a ketone and phosphoric acid by the method of using β zeolite as a catalyst, which is easy to separate and recover the catalyst and can be applied to a fixed bed. Without a by-product, the hydroxy-phenyl ether can be obtained in a high yield and the para-substituted product can be obtained preferentially compared to the ortho-substituted product. Similarly, alkyl-substituted phenols such as cresol and substituted phenol compounds such as sesamol can be produced.

The present invention is described in detail below.
In the benzene compound represented by the formula (1) and formula (2) used in the present invention, R ¹ represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and R 1 ² represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a halogen atom, n is an integer of 1 to 5, m is an integer of 1 to 5, n + m = 6, and a plurality of R ¹ And R ² may be the same or different, and p is an integer of 1 or 2.

Examples of the alkyl group having 1 to 6 carbon atoms of R ¹ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. These substituents include structural isomers.

Examples of the alkoxy group having 1 to 6 carbon atoms of R ¹ include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, and a hexyloxy group. These substituents include structural isomers.

  Preferred embodiments of the benzene compound represented by the formula (1) include alkylbenzenes such as methylbenzene, ethylbenzene, n-propylbenzene, isopropylbenzene, n-butylbenzene, t-butylbenzene, methoxybenzene (anisole), ethoxy Examples thereof include alkoxybenzenes such as benzene (phenetol), n-propoxybenzene, isopropoxybenzene, n-butoxybenzene, and t-butoxybenzene.

  The benzene compound represented by the formula (2) includes 1,2-methylenedioxybenzene (1,3-benzodioxole) when p is 1, and 1,2 when p is 2. 2-ethylenedioxybenzene (1,4-benzodioxane) is mentioned.

  Examples of the ketone used in the present invention include monoketone and diketone. Monoketones include acyclic or cyclic monoketones. Examples of the acyclic monoketone include linear or branched aliphatic monoketone and aromatic monoketone having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms. The hydrogen atom of these compounds may be substituted with a halogen atom (fluorine, chlorine, bromine or iodine). The number and position of halogen atoms are not particularly limited as long as they are not involved in the reaction.

  Examples of the linear aliphatic monoketone include acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-octanone, 2-nonanone, and 3-decanone. 6-undecanone, 2-tridecanone, 7-tridecanone, 2-tetradecanone, 2-pentadecanone, 2-hexadecanone, 2-heptadecanone, 3-octadecanone, 4-nonadecanone, 1-chloro-2-propanone, 1-chloro-3 -Heptanone, 1-bromo-3-heptanone.

  Examples of the branched aliphatic monoketone include 3-methyl-2-butanone, 3-methyl-2-pentanone, 4-methyl-2-pentanone, 3,3-dimethyl-2-butanone, 2,4-dimethyl- Examples include 3-pentanone, 6-methyl-2-heptanone, 2,6-dimethyl-4-heptanone, and 2,2,4,4-tetramethyl-3-heptanone. Examples of the aromatic monoketone include acetophenone, benzophenone, 1-phenyl-3-propanone, 1-phenyl-1-butanone, 1-phenyl-3-butanone, 1-phenyl-3-pentanone, 1,3-diphenyl- 2-propanone is mentioned.

  Examples of cyclic monoketones include cycloalkyl monoketones having 5 to 12 carbon atoms. The hydrogen atom of these compounds may be substituted with a halogen atom (fluorine, chlorine, bromine or iodine) or a substituent such as a linear or branched alkyl group having 1 to 6 carbon atoms. The number and position of the substituents are not particularly limited as long as they do not participate in the reaction. Examples of these compounds include cyclopentanone, cyclohexanone, cyclododecanone, 2-chlorocyclohexanone, 2-ethyl-1-cyclopentanone, and 2-methyl-1-cyclohexanone.

  Diketones include acyclic or cyclic diketones. Examples of the acyclic diketone include linear or branched aliphatic diketones and aromatic diketones having 5 to 21 carbon atoms, preferably 5 to 12 carbon atoms. The hydrogen atom of these compounds may be substituted with a halogen atom (fluorine, chlorine, bromine or iodine). The number and position of halogen atoms are not particularly limited as long as they are not involved in the reaction. Examples of the linear aliphatic diketone include 2,3-butanedione, 2,4-pentanedione, and 2,5-hexanedione. Examples of the branched aliphatic diketone include 2,5-dimethyl-3,4-hexanedione. Examples of the aromatic diketone include 1,2-diphenylethane-1,2-dione.

  Examples of the cyclic diketone include cyclic diketones having 5 to 12 carbon atoms. The hydrogen atom of these compounds may be substituted with a substituent such as a halogen atom (fluorine, chlorine, bromine or iodine) or a linear or branched alkyl group having 1 to 6 carbon atoms. The number and position of the substituents are not particularly limited as long as they do not participate in the reaction. Examples of the cyclic diketone include 1,4-cyclohexanedione.

  Preferred as the ketone used in the present invention is a linear or branched aliphatic monoketone, or a cyclic monoketone, and more preferred is a linear or branched aliphatic monoketone. Particularly preferred are 3-dimethyl-2-butanone (hereinafter referred to as pinacholine which is a common name), 4-methyl-2-pentanone, 3-pentanone, and 3,3-dimethyl-2-butanone.

  The amount of ketone used is preferably such that the molar ratio of ketone to peroxide (ketone: peroxide) is 0.2: 1 to 5: 1.

In the method for hydroxylating a substituted benzene compound using the proton type β zeolite of the present invention, a small amount of phosphoric acid is added to avoid the adverse effect of dissolved metal ions such as iron ions on the reaction. It doesn't matter.
Examples of phosphoric acid include o-phosphoric acid, pyrophosphoric acid, metaphosphoric acid, triphosphoric acid, tetraphosphoric acid, polyphosphoric acid, phosphoric anhydride, and phosphoric acid aqueous solution, and a phosphoric acid aqueous solution is preferable. The concentration of the phosphoric acid aqueous solution is preferably 0.001% by weight or more and less than 100% by weight.

  The amount of phosphoric acid used is such that the weight ratio of phosphoric acid to the benzene compound represented by formula (1) or (2) (phosphoric acid: benzene compound) is 0.0001: 1 to 0.05: 1. It is preferable.

  Examples of the peroxide used in the present invention include inorganic peroxides such as hydrogen peroxide, or ketone peroxides.

  Examples of the ketone peroxide include dialkyl ketone peroxide having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms. Examples of these compounds include dimethyl ketone peroxide, diethyl ketone peroxide, methyl ethyl ketone peroxide, methyl-n-propyl ketone peroxide, methyl isopropyl ketone peroxide, and methyl isobutyl ketone peroxide.

  As hydrogen peroxide, 0.1% by weight or more, preferably 0.1 to 90% by weight of hydrogen peroxide water can be used, but 30 to 80% by weight is more preferable.

  The peroxide used in the present invention is preferably hydrogen peroxide or ketone peroxide. This ketone peroxide can be synthesized by contacting a ketone with hydrogen peroxide, and the ketone used here is the same as described above.

  The amount of peroxide used is such that the molar ratio of peroxide to the benzene compound represented by the formula (1) or (2) (peroxide: benzene compound) is 1: 1 to 1: 100, and further 1: It is preferable that the range is 5 to 1:20.

  As a method for adding peroxide into the reaction system, it may be added all at once at the start of the reaction, but it may be added in several batches, or it may be added in small amounts continuously using a feed pump. You can also. In the case of divided addition, the amount of peroxide added per one time with respect to the benzene compound represented by the formula (1) or (2) is molar ratio, peroxide: benzene compound (1) or (2) = 2: 100 to 0.05: 100, more preferably 2: 100 to 0.1: 100. Moreover, in any case of divided addition and continuous addition, the amount of peroxide in the reaction system with respect to the benzene compound represented by the formula (1) or (2) is a molar ratio: peroxide: benzene compound (1 ) Or (2) = 2: 100 to 0.05: 100, more preferably 1: 100 to 0.1: 100.

The proton type β zeolite used in the present invention, in addition to the normal proton type β zeolite, has a temperature range of plus or minus 100 ° C. around 330 ° C. in the ammonia temperature programmed desorption method (NH ₃ -TPD) spectrum. Proton type β zeolite having an acid point showing a desorption peak and a strong acid point showing a desorption peak at 500 ° C. or higher of 2.5 μmol / g or less can be used.
In the present invention, these proton-type β zeolites, or alkaline earth metals, transition metals, group 2B metals, group 3B metals from the third period to the sixth period, group 4B metals from the fifth period to the sixth period, Or what carried metal loading, such as a lanthanoid metal, is used.

Among these proton-type β zeolites, there is an acid point showing a desorption peak in the range of plus or minus 100 ° C. around 330 ° C. in the spectrum of ammonia temperature programmed desorption method (NH ₃ -TPD), and 500 A proton type β zeolite having a strong acid point amount of 2.5 μmol / g or less exhibiting a desorption peak at or above ° C., or a product obtained by carrying the metal on this proton type β zeolite is preferred.

The proton type β zeolite is prepared by the method described in Non-Patent Document 6. For example, hydrothermal synthesis using a silicon source (silica gel, etc.), an aluminum source (sodium aluminate, pseudoboehmite, etc.), and an alkylammonium (tetraethylammonium hydroxide, etc.) as raw materials and firing Β zeolite (hereinafter referred to as AS (as-synthesized) β zeolite) obtained in an aqueous solution containing ammonium ions such as ammonium nitrate and ammonium chloride (ammonium salt concentration: 0.1 to 40% by weight) at 20 to 120 ° C. It is obtained by heat treatment for 1 to 20 hours, washing with ion-exchanged water, etc., drying at 20 to 150 ° C., and firing at 300 to 650 ° C. for 1 to 10 hours. Alternatively, the ASβ zeolite is immersed in a 0.01 N to 1 N hydrochloric acid aqueous solution, treated at room temperature to 100 ° C. for several minutes to several days, washed with ion-exchanged water, etc., dried at room temperature to 150 ° C., 150 Proton type β zeolite obtained by calcining at 650C to 650 ° C can also be suitably used.
In addition, ASβ zeolite may be prepared by the method described in Non-Patent Document 6 as described above, and a commercially available product can also be suitably used.
The content of aluminum (aluminum in the framework) in the ASβ zeolite is preferably such that Al: Si (atomic ratio) is 1:25 to 1: 10000. This ratio can be controlled by the composition of Si compound and Al compound, which are raw materials for ASβ zeolite, such as sodium silicate and sodium aluminate.

In the spectrum of ammonia temperature-programmed desorption method (NH ₃ -TPD), there is an acid point showing a desorption peak in the range of plus or minus 100 ° C. around 330 ° C. and a strong desorption peak at 500 ° C. or more. The proton type β zeolite having an acid point amount of 2.5 μmol / g or less is the above ASβ zeolite, proton type β zeolite not treated with an acidic aqueous solution, ammonium ion exchange type β zeolite, or alkali metal ion exchange type β-zeolite and the like are immersed in an acidic aqueous solution, then taken out, washed with water, dried, and calcined.

  Here, as the proton type β zeolite not subjected to the treatment with the acidic aqueous solution, a commercially available product or a proton type β zeolite newly prepared by the method described in Non-Patent Document 4 can be used.

  A commercially available thing can be used for an ammonium ion exchange type beta zeolite. The alkali metal ion exchange type β zeolite can be prepared by the method described in Non-Patent Document 6 in which proton type β zeolite is immersed in the metal ion-containing aqueous solution such as alkali metal nitrate, hydrochloride or sulfate. .

  Among these β zeolites, proton type β zeolite that has not been treated with the acidic aqueous solution is preferably used.

  The acid used as the acidic aqueous solution is not particularly limited, but includes aliphatic carboxylic acids (formic acid, acetic acid, propionic acid, citric acid, etc.), aromatic carboxylic acids (benzoic acid, etc.), amino acids (aspartic acid, glutamic acid). Etc.), or organic acids such as sulfonic acids (trifluoromethylsulfonic acid, etc.) or inorganic acids (nitric acid, phosphoric acid, hydrofluoric acid, hydrochloric acid, sulfuric acid, etc.), inorganic acids are preferred, and nitric acid is more preferred. preferable.

  As said acidic aqueous solution, what was adjusted to pH 0-6 is used. Further, the amount used is not particularly limited as long as the β zeolite is sufficiently immersed.

The immersion temperature of the β zeolite in the acidic aqueous solution is in the range of room temperature to 120 ° C, and preferably 40 to 90 ° C.
The immersion time is 1 to 12 hours.
This dipping operation is preferably performed with stirring, but a sufficiently similar effect can be obtained even when left standing.

  Next, the β zeolite immersed in the acidic aqueous solution is taken out and washed with water. Although the extraction method is not specifically limited here, For example, it is performed by methods, such as filtration. Moreover, as water used for water washing, ion-exchange water is preferable.

The washed β zeolite is dried.
The temperature range for drying is 90 to 150 ° C. The drying time is 1 hour to 2 days depending on the amount of β zeolite.

After this drying, the β zeolite is calcined. Although the temperature range of baking is 350-950 degreeC, 450-850 degreeC is preferable.
The firing time is 1 to 24 hours.

The proton-type β zeolite obtained by the above acidic aqueous solution treatment has an untreated spectrum of ammonia temperature programmed desorption method (NH ₃ -TPD, temperature rising rate 20 ° C./min, measuring range 100 ° C. to 700 ° C.). When compared with the above, the amount of strong acid points having a desorption peak in the range of plus or minus 100 ° C. around 330 ° C. and a desorption peak at 500 ° C. or higher is 2.5 μmol / g. Hereinafter, it is further characterized by being 0.0005 μmol / g (calculated from the detection limit of the desorption peak) or more and 2.5 μmol / g or less. In addition, the desorption peak around 200 ° C. of the untreated material is derived from physically adsorbed ammonia existing on the β zeolite structure due to dispersion force and the like, and is remarkably reduced by the acidic aqueous solution (see FIG. 2). .
Here, the amount of strong acid sites is calculated from the amount of desorbed ammonia in the ammonia temperature-programmed desorption method (NH ₃ -TPD) (see Non-Patent Document 9).

  In addition, this amount of desorbed ammonia is calculated according to the quantification method described in Non-Patent Document 8, with a desorption peak at 500 ° C. or higher at the bottom of the main peak centered at 330 ° C. being calculated from the previous main peak. They were separated by extension lines and quantified from the area (see FIG. 1 and the following formula 1).

  (A in the formula represents a main peak centered at 330 ° C., and B represents a desorption peak at 500 ° C. or higher. See FIG. 1.)

In addition, the proton type β zeolite of the present invention has a feature that the absorption at 3782 cm ⁻¹ is below the detection limit when the FT-IR spectrum is compared with that of an untreated one. (See Figure 3)

  Examples of the metal-supported proton-type β zeolite used in the present invention include the above-mentioned proton-type β zeolite, alkaline earth metal, transition metal, Group 2B metal, Group 3B metal from the 3rd period to the 6th period, and Period 5 to 6 A baked product carrying a periodic group 4B metal or a lanthanoid metal can be used. Examples of alkaline earth metals include beryllium, magnesium, calcium, strontium, and barium, with magnesium, calcium, strontium, and barium being preferred. Transition metals include 3A group such as scandium and yttrium, 4A group such as titanium and zirconium, 5A group such as vanadium and niobium, 6A group such as chromium, molybdenum and tungsten, 7A group such as manganese, iron, cobalt, nickel Group 1B such as copper, silver, and gold is preferable, and yttrium, niobium, tantalum, manganese, cobalt, nickel, and silver are preferable. Zinc is preferable as the group 2B metal. As the 3B group metal in the fourth period to the sixth period, gallium and indium are preferable. As the lanthanoid metal, lanthanum, cerium, praseodymium, samarium and ytterbium are preferable. In addition, tin and lead, which are Group 4B metals in the fifth to sixth periods, are preferable. As a metal loading method, a metal loading method such as a normal ion exchange method, an impregnation method, a chemical vapor deposition (CVD) method, or a mechanical kneading method can be applied, but an ion exchange method or an impregnation method is preferable.

The metal-supported proton-type β zeolite can be prepared by an ion exchange method according to the method described in Non-Patent Document 7, for example. For example, proton type β zeolite is heated at 20 to 120 ° C. for 1 to 20 hours in the metal ion-containing aqueous solution (the metal salt concentration: 0.1 to 40% by weight) such as nitrate, hydrochloride or sulfate of the metal. It is obtained by treating, washing with ion-exchanged water, etc., drying at 20 to 150 ° C. for 5 minutes to 24 hours, and firing at 300 to 650 ° C. for 1 to 10 hours. The metal ions supported on the proton-type β zeolite have an M ^{δ +} / Al (δ represents an integer of 1, 2 or 3) of 0.0001 to 10, more preferably 0.01 to 1 (M ^{δ +} It represents a metal ion, and Al is preferably in a range such that the ratio (atomic ratio) of aluminum in the framework of proton type β zeolite is obtained.

  The metal-supported proton type β zeolite by the impregnation method can be performed by the method described in Non-Patent Document 7, or the like. For example, it can be prepared by the method shown below. A predetermined amount of a solution in which an inorganic salt such as a metal nitrate, hydrochloride or sulfate, or an organic salt such as an alkoxide is dissolved in an arbitrary solvent is impregnated in a pre-calcined β zeolite. This is stirred and heated at 90 to 140 ° C. to evaporate the solvent, and then baked at 300 to 650 ° C. for 1 to 10 hours. At this time, a method using a beaker or a magnetic crucible is preferably used for the impregnation operation. However, the impregnation may be performed by a method in which a carrier is placed in a solution using a rotary evaporator, and the solvent is removed under reduced pressure and dried. The metal supported on the proton-type β zeolite has an M / Al ratio of 0.01 to 1000, more preferably 0.1 to 100 (M represents a supported metal, and Al represents aluminum introduced into the skeleton). It is preferable that the range is such that (atomic ratio).

  The amount of the proton type β zeolite used is such that the weight ratio of the proton type β zeolite to the benzene compound represented by the formula (1) or (2) (proton type β zeolite: benzene compound) is 1: 1 to 1: 500, Is preferably in the range of 1: 5 to 1: 100.

  Examples of the shape of the proton-type β zeolite used in the present invention include powders, granules, pellets, and honeycomb shaped bodies.

  As a shape according to the manufacturing method of the phenol compound shown by said Formula (3) or Formula (4), when manufacturing using a liquid phase batch type reactor, powder, a granule, etc. are used, for example. Preferably, when a liquid phase flow reactor is used, pellets, honeycomb shaped bodies and the like are preferable.

  In the production of the phenol compound represented by formula (3) or formula (4) of the present invention, the reaction temperature is preferably 20 to 300 ° C, more preferably 40 to 200 ° C. The reaction time varies depending on the type of catalyst and the reaction temperature, but is not particularly limited. The reaction can be performed at atmospheric pressure, but may be performed under reduced pressure or increased pressure. The reaction can be carried out in a liquid phase by a batch system, a flow system, a trickle bed system, or the like.

  As the reaction in the present invention, for example, a benzene compound represented by the above formula (1) or formula (2), hydrogen peroxide, ketone and phosphoric acid are supplied to a reactor pre-filled with β zeolite, and the above formula ( Examples thereof include a reaction in which a benzene compound represented by 1) or formula (2) is oxidized to produce a phenol compound represented by formula (3) or formula (4), and the reaction mixture is discharged from the reactor.

  The phenol compound represented by the formula (3) or the formula (4) produced in the present invention corresponds to the structure of the benzene compound represented by the formula (1) or the formula (2) of the raw material, and one kind or several kinds As a mixture of These phenol compounds can be obtained by separation and purification by a conventional method.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. In addition, this invention is not restrict | limited by these Examples.
The yield of the phenol compound is determined according to the following formula. The analysis was performed by gas chromatography.

Reference Example 1 Treatment of proton type β zeolite with acidic aqueous solution 10.0 g of proton type β zeolite made by Zeolis (hereinafter referred to as H / β) with Al: Si = 1: 37.5 was added to an aqueous nitric acid solution having a pH of 1.3. This was placed in an eggplant flask containing 50 ml and heated for 2 hours while stirring at 85 ° C. in an oil bath. Next, the zeolite was sufficiently washed with ion-exchanged water, filtered with suction, dried at 110 ° C., and calcined at 550 ° C. for 2.5 hours. When the obtained β zeolite (hereinafter referred to as H / βHNO ₃ ) was subjected to ICP emission analysis, aluminum in the β zeolite was partially removed and Al: Si = 1: 78.

Reference Example 2 Preparation of calcium-supporting proton type β zeolite 15 ml of Ca ion-containing aqueous solution was prepared by dissolving 1.8 g of calcium nitrate tetrahydrate in ion-exchanged water. Ion exchange between protons and calcium ions was performed by immersing 2 g of Zeolist proton type β-zeolite having Al: Si = 1: 37.5 in the obtained aqueous solution and keeping it at 85 ° C. for 14 hours. The obtained suspension was filtered with suction, dried at 110 ° C., and then calcined at 550 ° C. for 2.5 hours to obtain 1.9 g of calcium-supported proton type β zeolite (hereinafter referred to as Ca / H / β). To do). As a result of ICP emission analysis, the ratio (atomic ratio) between calcium and Al introduced into the β zeolite was Ca / Al = 0.28.

Reference Example 3 Calcium supported on proton type β zeolite treated with acidic aqueous solution A catalyst supporting calcium with respect to H / βHNO ₃ was prepared in the same manner as in Reference Example 2 (hereinafter Ca / H / βHNO ₃ ). As a result of ICP emission analysis, the ratio (atomic ratio) between calcium and Al introduced into the β zeolite was Ca / Al = 0.41.

Example 1.
0.50 g of Zeolist proton type β zeolite with Al: Si = 1: 37.5, 46.0 g (0.425 mol) of anisole, 1.06 g of pinacholine (3,3-dimethyl-2-butanone) 0106 mol), 0.02 g of 85 wt% phosphoric acid aqueous solution was placed in a 300 ml flask and the atmosphere was replaced with a nitrogen atmosphere, and then the temperature was raised to 120 ° C. while stirring in an oil bath. Next, at this temperature, 0.10 g of 60% hydrogen peroxide solution was dropped, and 0.10 g was dropped every 3 minutes, 6 minutes, 9 minutes, 12 minutes, and 15 minutes later. A total of 0.60 g (0.0106 mol) of hydrogen peroxide was added in 6 portions. The reaction was continued until 60 minutes after the first addition.

  As a result, the yield of methoxyphenol was 35.0% for o-methoxyphenol and 49.0% for p-methoxyphenol, and the total yield was 84.0%. The reaction solution was only colored light reddish brown, and tar accumulation was hardly observed.

Example 2
The reaction was conducted in the same manner as in Example 1 except that the catalyst was H / βHNO ₃ prepared in Reference Example 1.
As a result, the yield of methoxyphenol was 35.8% for o-methoxyphenol and 52.2% for p-methoxyphenol, and the total yield was 88.0%. The reaction solution was only colored light red and tar accumulation was hardly observed.

Example 3
The reaction was conducted in the same manner as in Example 1 except that the catalyst was Ca / H / β prepared in Reference Example 2.
As a result, the yield of methoxyphenol was 36.4% for o-methoxyphenol and 51.9% for p-methoxyphenol, and the total yield was 88.3%. The reaction solution was only colored light red and tar accumulation was hardly observed.

Example 4
The reaction was carried out in the same manner as in Example 1 except that the catalyst was Ca / H / βHNO ₃ prepared in Reference Example 3.
As a result, the yield of methoxyphenol was 35.0% for o-methoxyphenol and 50.2% for p-methoxyphenol, and the total yield was 85.2%. The reaction solution was only colored light red and tar accumulation was hardly observed.

Comparative Example 1
The reaction was conducted in the same manner as in Example 1 except that 0.02 g of 98% concentrated sulfuric acid was used.
As a result, the yield of methoxyphenol was 21.6% for o-methoxyphenol and 3.8% for p-methoxyphenol, and the total yield was 25.4%. The reaction solution colored reddish brown, and accumulation of tar content was observed.

Comparative Example 2
The reaction was performed in the same manner as in Example 1 except that the catalyst was US-Y made by JGC Universal Co., which had Al: Si = 1: 3.0.
As a result, the yield of methoxyphenol was 34.9% for o-methoxyphenol and 12.2% for p-methoxyphenol, and the total yield was 47.1%. The reaction solution was only colored light red and almost no tar content was observed.

Comparative Example 3
The catalyst was TS-1 manufactured by N.E. Chemcat having Ti: Si = 1: 38.0, and the reaction was conducted in the same manner as in Example 1 except that pinacholine and phosphoric acid were not added.
As a result, the yield of methoxyphenol was 4.2% for o-methoxyphenol and 14.9% for p-methoxyphenol, and the total yield was 19.1%. The reaction solution was only colored light red and almost no tar content was observed.

Embodiment 5 FIG.
A 300 ml flask containing 0.20 g of the proton-treated β zeolite prepared in Reference Example 1, 11.5 g (0.106 mol) of anisole, 0.27 g (0.00321 mol) of diethyl ketone and 0.02 g of 85 wt% phosphoric acid aqueous solution And the atmosphere was heated to 120 ° C. while stirring in an oil bath. Next, at this temperature, 0.10 g of a 60% hydrogen peroxide solution was dropped, and after 3 minutes and 6 minutes, another 0.10 g was dropped, and a total of 0.30 g (0.00529 mol) of hydrogen peroxide solution was added. Was added in three portions. After 10 minutes, the temperature of the oil bath was raised to 140 ° C., and the reaction was continued until 60 minutes from the first addition.
As a result, the yield of methoxyphenol was 32.6% for o-methoxyphenol and 44.4% for p-methoxyphenol, and the total yield was 77.0%. The reaction solution was only colored light reddish brown, and tar accumulation was hardly observed.

Example 6
The reaction was conducted in the same manner as in Example 4 except that 0.63 g (0.00629 mol) of methyl isobutyl ketone (4-methyl-2-pentanone) was used.
As a result, the yield of methoxyphenol was 34.6% for o-methoxyphenol and 37.9% for p-methoxyphenol, and the total yield was 72.5%. The reaction solution was only colored light reddish brown, and tar accumulation was hardly observed.

Example 7
The reaction was conducted in the same manner as in Example 4 except that the ketone was 0.32 g (0.00319 mol) of pinacholine (3,3-dimethyl-2-butanone).
As a result, the yield of methoxyphenol was 33.5% for o-methoxyphenol and 46.4% for p-methoxyphenol, and the total yield was 79.9%. The reaction solution was only colored light reddish brown, and tar accumulation was hardly observed.

Example 8
The reaction was carried out in the same manner as in Example 5 except that 0.20 g of proton type β zeolite made by Zeolis with Al: Si = 1: 75 was used as a catalyst, and phosphoric acid was not added.
As a result, the yield of methoxyphenol was 30.3% for o-methoxyphenol and 40.2% for p-methoxyphenol, and the total yield was 70.5%. The reaction solution was only colored light reddish brown, and tar accumulation was hardly observed.

Example 9
The reaction was conducted in the same manner as in Example 1 except that 52.0 g (0.425 mol) of phenetole (ethoxybenzene) was used as a reaction substrate instead of anisole.
As a result, the yield of ethoxyphenol was 32.5% for o-ethoxyphenol and 46.1% for p-ethoxyphenol, and the total yield was 78.6%. The reaction solution was only colored light red and almost no tar content was observed.

Example 10
0.20 g of H / βHNO ₃ prepared in Reference Example 1, 9.80 g of toluene, 0.27 g of 3-pentanone, and 0.02 g of 85 wt% phosphoric acid aqueous solution were placed in a 300 ml flask, replaced with a nitrogen atmosphere, and stirred. The temperature was raised to 120 ° C. Next, at this temperature, 0.10 g of 60% by weight hydrogen peroxide solution is dropped, and after 1.5 g, 0.10 g is further dropped, and further 0.10 g is dropped after 3 minutes. Reacted until.
As a result, the yield of o-cresol, an oxidation product of toluene, was 16.2%, the yield of p-cresol was 19.5%, and the total yield of cresol was 35.7%.

Example 11
The reaction was conducted in the same manner as in Example 9 except that 0.34 g of 3-pentanone was changed to pinacholine (3,3-dimethyl-2-butanone).
As a result, the yield of o-cresol which is an oxidation product of toluene was 20.3%, the yield of p-cresol was 21.9%, and the total yield of cresol was 42.2%.

Example 12 FIG.
A 300 ml flask containing 0.50 g of H / βHNO ₃ prepared in Reference Example 1, 52.0 g (0.412 mol) of methylenedioxybenzene, 2.16 g (0.022 mol) of pinacholine, and 0.02 g of 85 wt% phosphoric acid aqueous solution. Then, the temperature was raised to 100 ° C. with stirring. Next, at this temperature, 0.10 g of 60 wt% hydrogen peroxide water was added dropwise, 1.5 minutes later 0.10 g, 3 minutes further 0.10 g, 4.5 minutes later 0.10 g, 6 minutes Thereafter, 0.10 g was added dropwise, and 0.10 g was added dropwise after 7.5 minutes, and the reaction was continued until 30 minutes from the first addition.
As a result, the yield of sesamol was 28.0%.

Spectrum of proton-type beta zeolite by ammonia temperature programmed desorption (NH ₃ -TPD) (schematic diagram) Spectra of ammonia temperature programmed desorption method (NH ₃ -TPD) of H / β (38) and H / βHNO ₃ (38) FT-IR spectra of H / β (38) and H / βHNO ₃ (38)

Claims (4)

In the presence of proton type β zeolite and ketone, at least one selected from the group consisting of benzene compounds represented by the following formulas (1) and (2):

(In the formula, R ¹ represents an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and R ² represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a halogen atom. , N is an integer of 1 to 5, m is an integer of 1 to 5, n + m = 6, the plurality of R ¹ and R ² may be the same or different, and p is 1 or 2 (It is an integer.)
A method for producing at least one phenol compound selected from the group consisting of phenol compounds represented by the following formulas (3) and (4), characterized by oxidation with a peroxide.

(Wherein R ¹ , R ² , n and p are as defined above, and m ′ = m−1). The method for producing a phenol compound according to claim 1, wherein the peroxide is hydrogen peroxide or ketone peroxide. The proton-type β zeolite has an acid point that exhibits a desorption peak in the range of plus or minus 100 ° C. around 330 ° C. in the ammonia temperature programmed desorption method (NH ₃ -TPD) spectrum, and 500 ° C. or more. 3. The method for producing a phenol compound according to claim 1 or 2, which is a proton-type β zeolite having an amount of strong acid sites showing a desorption peak of 2.5 μmol / g or less. Proton type β zeolite is alkaline earth metal, transition metal, group 2B metal, group 3B metal from the 3rd period to the 6th period, group 4B metal from the 5th period to the 6th period, or a lanthanoid metal supported proton type β zeolite The manufacturing method of the phenolic compound of Claim 1 or 2.

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