JP2560216B2 - Process for producing alkyl-substituted aromatic compound - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing an alkyl-substituted aromatic compound by introducing an alkyl group into the aromatic nucleus of the aromatic compound.

[Prior Art] An aromatic compound having an alkyl group as a substituent is useful as an intermediate for producing substances used for various purposes. For example, 2,6-dialkylnaphthalene having an alkyl group at the β-position of naphthalene, such as 2-methyl-6-isopropylnaphthalene, has heat resistance, mechanical strength, and dimensional stability by oxidizing its side chain. 6-Hydroxy-2-naphthoic acid and naphthalene-2,6-dicarboxylic acid useful for producing a polyester having excellent performance in terms of corrosion resistance and the like can be easily produced.

As a method for producing such an alkyl-substituted aromatic compound, a Friedel-Crafts reaction or a solid silica-alumina catalyst in which alkylation is carried out by a liquid phase reaction using anhydrous aluminum chloride, boron trifluoride, iron oxide or the like has been conventionally used. A gas phase reaction and the like using is known. However,
In the case of Friedel-Crafts reaction, in general, a relatively large amount of high-boiling compounds is generated as a by-product of the reaction, and a washing neutralization step for decomposing the catalyst is required as a post-treatment after the reaction. In this case, there is a problem that a large amount of acidic waste liquid is generated, the catalyst cannot be reused, and the catalyst is hygroscopic and difficult to handle. Further, the gas phase reaction using the solid silica-alumina catalyst also requires a high temperature, and many side reactions occur, resulting in poor yield and selectivity of the target product.

[Problems to be Solved by the Invention] The present invention was devised in view of such a viewpoint, and an object thereof is to eliminate the problem of acidic waste liquid in the post-treatment after completion of the reaction, and to provide a catalyst. To provide a process for producing an alkyl-substituted aromatic compound, which is easy to handle and can be reused, and which can improve the yield and selectivity of the target product by reaction under mild conditions. It is in.

[Means for Solving the Problem] That is, the present invention provides a periodic table IVa and / or IV obtained by mixing a plurality of types of metal compounds in an organic solvent having a coordination ability and hydrolyzing the mixture. A method for producing an alkyl-substituted aromatic compound, which comprises reacting an aromatic compound with an alkylating agent in the presence of a composite metal catalyst containing a group b metal oxide (excluding silica-alumina catalyst).

The composite metal catalyst used in the present invention is a catalyst composed of a plurality of types of metal oxides containing at least one type IVa and / or IVb metal oxide of the periodic table. It is necessary that the metal oxide is prepared by a method of mixing a plurality of types of metal compounds in an organic solvent having a coordinating ability and then hydrolyzing them, a so-called compound mixing method (or sol-gel method). Is.

Even if the metal oxide contained in this composite metal catalyst is a combination of two or more kinds of oxides of metals of group IVa and / or IVb of the periodic table, the metal oxide of the group IVa and / or IV of the periodic table is used. It may be a combination of an oxide of a Group IVb metal and another metal oxide. And the above-mentioned periodic table IVa and / or IVb
The group metal oxide is preferably an oxide of titanium, zirconium or silicon, specifically an oxide of titanium oxide, zirconium oxide, silicon oxide or the like, more preferably titanium dioxide, zirconium dioxide or dioxide. It is silicon (silica). Further, as the metal oxide other than the oxides of the metal of group IVa and / or IVb of the Periodic Table contained in the above-mentioned composite metal catalyst, preferably, it is an oxide of aluminum, specifically, aluminum oxide. (Alumina) and the like. These Periodic Tables IVa and / or IV
Regarding the oxide of the group b metal or other metal oxide, only one kind thereof may be used, or a mixture of two or more kinds thereof may be used.

When a metal oxide of group IVa and / or IVb of the periodic table in this composite metal catalyst is used in combination with another metal oxide, the ratio (weight ratio: IVa & IV
(B metal oxide / other metal oxide) is not particularly limited as long as there is an effective amount of a group IVa and / or IVb metal oxide of the periodic table as a catalyst, but preferably 0.01 ˜5, more preferably 0.02 to 1 is preferable.

And, such a composite metal catalyst is described in the periodic table
A mixture of multiple hydrolyzable metal compounds containing Group IVa and / or IVb metals or other metals is mixed well in an organic solvent having coordination ability, and water is added to this to hydrolyze. It is prepared by drying, drying, and baking.

Periodic Table IVa used in the preparation of this composite metal catalyst
As the metal compound containing a Group IVb metal, and / or if it can be hydrolyzed, it is preferably methoxide, ethoxide, from the viewpoint of the ease of handling and post-treatment, and the like.
Various alkoxides such as n-propoxide, isopropoxide, sec-butoxide and the like. Further, the metal compound containing a metal other than the Group IVa and / or IVb metal of the Periodic Table is not particularly limited as long as it is hydrolyzable, but may be handled or post-treated. From the viewpoint of easiness and the like, preferably methoxide, ethoxide, n-
Various alkoxides such as propoxide, isopropoxide, sec-butoxide, etc., and chelate complexes such as acetylacetone aluminum and acetoacetate aluminum dibutoxide can also be used as the alumina raw material.

Further, the organic solvent used again for producing the composite metal catalyst needs to be capable of uniformly mixing the plurality of types of metal compounds, and for this purpose, the metal compound was added to the organic solvent. At that time, it is necessary that the molecules constituting the organic solvent coordinate with the metal compound to uniformly disperse the metal compound in the organic solvent. Ability is required. Such organic solvents include monohydric alcohols such as methanol, ethanol and propanol, ethylene glycol, 1,2-propanediol, 1,2
-Butanediol, 1,2-pentanediol, 1,2-hexanediol, styrene glycol, 2-methyl-1,2
-Propanediol, 2,3-butanediol, pinacol, 3,3-dimethyl-1,2-butanediol, 1,2-cyclohexanediol, 1,3-propanediol, 1,3-butanediol, 3-methyl -1,3-butanediol, hexylene glycol, 2,4-pentanediol, 2-methyl-2,4-pentanediol, 2,2-dimethyl-1,3-
Propanediol, 2-methyl-2-propyl-1,3-
Propanediol, 2,2-diethyl-1,3-propanediol, 2-ethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,3-cyclohexanediol, 1 , 4-butanediol, 2,5-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1,4-
Cyclohexanediol, 1,5-pentanediol, 1,6
-Dihydric or polyhydric alcohols such as hexanediol, 1,2-decanediol, 1,10-decanediol, 1,12-dodecanediol, glycerol, amino alcohols such as aminoethyl alcohol, hydroxyacetone, 1-
Hydroxyl-3-butanone, kettle alcohols such as diacetone alcohol, acetylacetone, diacetyl,
Examples thereof include diketones such as benzoylacetone, and ketoesters such as ethyl acetoacetate, ethyl pyruvate, ethyl benzoylacetate and ethyl benzoylformate, and these can be used alone or in combination.
Further, in producing the composite metal catalyst, other additives such as a chelating agent and an inorganic acid or its ester may be added, and examples of the chelating agent include 1,2- or 1,3
-Diketones, α-ketoesters, β-ketoesters, malonic acid esters and the like, and inorganic acids and their esters include sulfuric acid esters such as hydrochloric acid and dimethyl sulfate, and phosphoric acid esters.

Using such an organic solvent and other additives to be added as necessary, the reaction conditions for mixing and hydrolyzing a plurality of kinds of metal compounds are not particularly limited, but the reaction temperature is not limited. Is usually 20 ~ in terms of reaction rate
The range of 150 ° C., preferably 40 to 80 ° C. is good, and the amount of water to be added is too small, the hydrolysis is insufficient, and if it is too large, a strong gel is not formed. 1 to 100 relative to 1 mole of the metal compound
Mol, preferably in the range of 2 to 30 mol. Drying of the formed gel may be performed by any method, for example, using a rotary evaporator under reduced pressure at 50 to 200 ° C.
, A dry gel of the composite metal catalyst is obtained. Furthermore, the dried gel of the composite metal catalyst thus obtained is then pulverized and subjected to usual conditions, for example, 400 to 800
° C, preferably 450-700 ° C for 1-20 hours, preferably 2 hours.
Calcination is performed under the conditions of 1212 hours to obtain a composite metal catalyst.

In the present invention, an alkyl-substituted aromatic compound is produced by reacting an aromatic compound with an alkylating agent in the presence of the thus prepared composite metal catalyst.

The aromatic compound to which the method of the present invention is applied may be one having a substitution position to be alkylated on the benzene ring in the molecule, such as benzene, biphenyl and diphenylmethane. It may be an independently existing type, or a type having a condensed ring structure such as naphthalene and anthracene. It may be an alkyl-substituted aromatic compound having more alkyl groups introduced.
Particularly preferable aromatic compound in the method of the present invention is 2-alkylnaphthalene such as 2-methylnaphthalene, since the method of the present invention is an alkylation reaction excellent in selectivity under mild conditions. It is useful for the production of 6,6-dialkylnaphthalene.

Examples of the alkylating agent include olefins such as ethylene and propylene, alcohols such as ethanol and isopropyl alcohol, ethers such as ethyl ether and isopropyl ether, esters such as ethyl acetate and isopropyl acetate, methyl chloride and isopropyl chloride. Alkylating agents used in ordinary alkylation reactions such as halogenated alkyls, and polyalkylbenzenes such as diethylbenzene, triethylbenzene, tetraethylbenzene, diisopropylbenzene triisopropylbenzene, and tetraisopropylbenzene, and mixtures thereof. Examples thereof include an alkylating agent used in the transalkylation reaction.

The reaction for producing an alkyl-substituted aromatic compound by the method of the present invention may be a flow reaction type or a batch reaction type, but in the case of mass production at an industrial level, a catalyst fixed bed may be used. The distribution reaction form of is suitable. The reaction conditions may be appropriately selected depending on the type of the aromatic compound used as the raw material and the alkylating agent, whether or not the reaction solvent is used, and for example, olefins are used as the alkylating agent. In the case of the reaction under pressure in the liquid phase, high-boiling saturated hydrocarbons such as decalin, cyclododecane, decane, undecane and dodecane are used as the reaction solvent, and the reaction temperature is 150 to 300 ° C, preferably 200 to 280 ° C and the reaction pressure. (Olefin pressure) ^{2 to 20} kg / cm ² · G, preferably 3 to 10 kg / cm ² · G.

[Examples] Hereinafter, the method of the present invention will be specifically described based on Examples.

[Preparation of Composite Metal Catalyst] (1) ZrO ₂ —SiO ₂ Catalyst (Zr—Si) 14.38 g of zirconium / n-propoxide and 45.73 g of tetraethoxysilane were stirred and mixed, and then 2-methyl-2,4 -64.86 g of pentanediol, 0.79 g of dimethyl sulfate and 30 ml of ethanol were added and mixed by stirring at 60 ° C for 3 hours. 15.82 g of water and 20 ml of ethanol in the obtained mixed solution.
Was added, the temperature was raised to 80 ° C., and hydrolysis was performed for 18 hours with stirring. The reaction mixture gelled and gelatinized. The gelled reaction mixture was dried by a rotary evaporator, pulverized and then calcined at 550 ° C. for 8 hours to obtain 20 g of a ZrO ₂ —SiO ₂ catalyst having a molar ratio (ZrO ₂ / SiO ₂ ) of 0.2. Also,
By the same method, molar ratios of 1, 0.5, 0.1, 0.04 and 0.02
ZrO ₂ —SiO ₂ catalyst was prepared.

(2) ZrO ₂ —SiO ₂ catalyst (Zr—Si) 14.38 g of zirconium n-propoxide and 22.85 g of ethyl acetoacetate (AAE) were added to 20 ml of ethanol, and 60
Stir for 30 minutes at ℃, and then add tetraethoxysilane 18.2
9g, dimethyl sulfate 0.79g, ethylene glycol (EG) 34.
06 g and 10 ml of ethanol were added, and the mixture was stirred at 60 ° C. for 3 hours and mixed. 15.82 g of water and 20 ml of ethanol were added to the obtained mixed solution, the temperature was raised to 80 ° C., and hydrolysis was performed for 18 hours with stirring. The reaction mixture gelled and gelatinized. The gelled reaction mixture was dried on a rotary evaporator, ground and then calcined at 550 ° C. for 8 hours,
A ZrO ₂ —SiO ₂ catalyst with a molar ratio of (ZrO ₂ / SiO ₂ ) 0.5 was obtained. Further, as a reaction solvent, pinacol (PI), 3-methyl-1,
The molar ratio of 3-butanediol (MBO) or a mixed solvent of ethylene glycol and biacetyl (BA) of 5: 4 is used.
A 0.5 ZrO ₂ —SiO ₂ catalyst was prepared.

(3) TiO ₂ —SiO ₂ catalyst (Ti—Si) After stirring and mixing 13.90 g of titanium isopropoxide and 50.95 g of tetraethoxysilane, 2-methyl-2,4-
86.71 g of pentanediol, 0.79 g of dimethyl sulfate and 30 ml of ethanol were added, and the mixture was stirred at 60 ° C. for 3 hours and mixed.
21.15 g of water and 20 ml of ethanol were added to the obtained mixed solution, the temperature was raised to 80 ° C., and hydrolysis was performed for 18 hours with stirring. The reaction mixture gelled and gelatinized.
The gelled reaction mixture was dried with a rotary evaporator, pulverized and then calcined at 550 ° C. for 8 hours to give a molar ratio (TiO 2
20 g of TiO ₂ —SiO ₂ catalyst of ₂ / SiO ₂ ) 0.2 was obtained. A TiO ₂ —SiO ₂ catalyst having a molar ratio of 0.5 was prepared by the same method.

(4) TiO ₂ —SiO ₂ catalyst (Ti—Si) 13.90 g of titanium isopropoxide and 22.85 g of ethyl acetoacetate (AAE) were added to 20 ml of ethanol, and the mixture was added at 30 ° C. at 60 ° C.
After stirring for 2 minutes, 20.38 g of tetraethoxysilane, 0.79 g of dimethyl sulfate, 34.06 g of ethylene glycol (EG) and 10 ml of ethanol were added, and the mixture was stirred at 60 ° C. for 3 hours and mixed. 15.82 g of water and 20 ml of ethanol in the obtained mixed solution.
Was added, the temperature was raised to 80 ° C., and hydrolysis was performed for 18 hours with stirring. The reaction mixture gelled and gelatinized. The gelled reaction mixture was dried by a rotary evaporator, pulverized and then calcined at 550 ° C. for 8 hours to obtain a TiO ₂ —SiO ₂ catalyst having a molar ratio (TiO ₂ / SiO ₂ ) 0.5.

(5) ZrO ₂ -TiO ₂ catalyst (Zr-Ti) 12.16 g of zirconium n-propoxide and 21.10 g of titanium isopropoxide were stirred and mixed, and then 65.80 g of 2-methyl-2,4-pentanediol, Dimethyl sulfate 0.79 g
And 30 ml of ethanol, and the mixture was stirred at 60 ° C. for 3 hours and mixed. 16.05 g of water and 20 ethanol were added to the obtained mixed solution.
ml was added, the temperature was raised to 80 ° C., and hydrolysis was performed for 18 hours with stirring. The reaction mixture gelled and gelatinized. The gelled reaction mixture was dried by a rotary evaporator, pulverized and then calcined at 550 ° C. for 8 hours to obtain a ZrO ₂ —TiO ₂ catalyst having a molar ratio (ZrO ₂ / TiO ₂ ) 0.5. In addition, ZrO ₂ —TiO ₂ catalysts with molar ratios of 1, 0.2 and 0.1 were prepared by the same method.

_{(6) TiO 2 -Al 2 O} 3 catalyst (Ti-Al) followed by stirring and mixing the aluminum · sec-butoxide 40.52g titanium isopropoxide 4.68 g, thereto 2-methyl-2,4-pentanediol 53.46g , Dimethyl sulfate 0.79 g
And 30 ml of ethanol, and the mixture was stirred at 60 ° C. for 3 hours and mixed. 13.04 g of water and 20% of ethanol were added to the obtained mixed solution.
ml was added, the temperature was raised to 80 ° C., and hydrolysis was performed for 18 hours with stirring. The reaction mixture gelled and gelatinized. The gelled reaction mixture was dried by a rotary evaporator, pulverized and then calcined at 550 ° C. for 8 hours to obtain a TiO ₂ —Al ₂ O ₃ catalyst having a molar ratio (TiO ₂ / Al ₂ O ₃ ) 0.2. Also,
In a similar manner, TiO _{2 with} molar ratios of 1, 0.5, 0.1 and 0.05
The -al ₂ O ₃ catalyst 20g was prepared.

[Isopropylation reaction of 2-methylnaphthalene] Examples 1 to 22 5.5 g (38.7 mmol) of 2-methylnaphthalene (2-MN) and 20 ml of n-undecane in an autoclave having an internal volume of 80 ml.
And 2.5 g of catalyst were charged, and the inside of this autoclave was sufficiently replaced with propylene gas, and the propylene pressure was 5 kg / cm ^2.
The reaction was carried out for 7 hours under stirring at G and a reaction temperature of 240 ° C.

After the completion of the reaction, the catalyst was removed by filtration, and the composition of the obtained reaction mixture was examined by gas chromatography. The conversion of 2-methylnaphthalene, the selectivity and yield of methylisopropylnaphthalene (MIPN), Its 2,6-isomer in isopropyl naphthalene and
The proportion occupied by the sum of the 2,7-isomers, and the selectivity and yield of methyldiisopropylnaphthalene (MDIPN) were examined. The results are shown in Table 1.

[Ethylation reaction of naphthalene] Example 23 26.11 g of zirconium n-propoxide and 41.49 g of ethyl acetoacetate were added to 20 ml of ethanol and stirred at 60 ° C for 30 minutes, and further 33.21 g of tetraethoxysilane and dimethyl sulfate were added. 0.79 g, 24.74 g of ethylene glycol and 10 ml of ethanol were added, and the mixture was stirred at 60 ° C. for 3 hours and mixed. To the resulting mixed solution was added water 11.49g and ethanol 20ml,
The temperature was raised to 80 ° C. and hydrolysis was performed for 18 hours with stirring. The reaction mixture gelled and gelatinized. The gelled reaction mixture was dried on a rotary evaporator, crushed and then calcined at 550 ° C. for 8 hours to give a molar ratio (ZrO ₂ /
20 g of ZrO ₂ —SiO ₂ catalyst with SiO ₂ ) 0.5 was obtained.

2.5 g of the catalyst thus obtained and 5 g of naphthalene (3
8.7 mmol, 1.81 g (39.2 mmol) of ethanol and 20 ml of n-undecane were charged into an autoclave having an internal volume of 80 ml and reacted at a reaction temperature of 240 ° C. for 7 hours with stirring. After completion of the reaction, the obtained reaction product was analyzed by gas chromatography to find that the conversion of naphthalene was 59% and the selectivity and yield of ethylnaphthalene were 70% and 41%, respectively.
Thus, the proportion of 2-ethyl compound in the produced etalnaphthalene was 60%.

Example 24 After 26.11 g of zirconium n-propoxide and 33.21 g of tetraethoxysilane were mixed with stirring, 0.79 g of dimethyl sulfate, 46.30 g of 1.2-cyclohexanediol and 30 ml of ethanol were added thereto, and the mixture was stirred at 60 ° C. for 3 hours. Mixed.
11.49 g of water and 20 ml of ethanol were added to the obtained mixed solution, the temperature was raised to 80 ° C., and hydrolysis was performed for 18 hours with stirring. The reaction mixture solidified into a gelled gelatinous form.
The gelled reaction mixture was dried on a rotary evaporator, crushed and then calcined at 550 ° C. for 8 hours to give a molar ratio (ZrO 2
20 g of a ZrO ₂ —SiO ₂ catalyst of ₂ / SiO ₂ ) 0.5 was obtained.

2.5 g of the catalyst thus obtained and 5 g of naphthalene (3
(8.7 mmol) and n-undecane (20 ml) were charged into an autoclave with an internal volume of 80 ml, and the inside of the container was sufficiently replaced with ethylene gas, and then the ethylene pressure was 2.5 kg / cm ² · G and the reaction temperature was 240 ° C for 7 hours. The reaction was carried out with stirring. After completion of the reaction, the obtained reaction product was analyzed by gas chromatography. As a result, the naphthalene conversion rate was 38%, the ethylnaphthalene selectivity and yield were 73% and 28%, respectively,
In the generated etalnaphthalene, the proportion of 2-ethyl compound is
It was 80%.

Example 25 After 26.11 g of zirconium n-propoxide and 33.21 g of tetraethoxysilane were stirred and mixed, 0.79 g of dimethyl sulfate, 35.14 g of 3-methyl-1,3-diol and 30 ml of ethanol were added thereto, and the mixture was heated at 60 ° C. Stir for 3 hours and mix. To the resulting mixed solution was added water 11.49g and ethanol 20ml,
The temperature was raised to 80 ° C. and hydrolysis was performed for 18 hours with stirring. The reaction mixture gelled and gelatinized. The gelled reaction mixture was dried on a rotary evaporator, crushed and then calcined at 550 ° C. for 8 hours to give a molar ratio (ZrO ₂ /
20 g of ZrO ₂ —SiO ₂ catalyst with SiO ₂ ) 0.5 was obtained.

2.5 g of the catalyst thus obtained and 5 g of naphthalene (3
8.7 mmol, 1.81 g (39.2 mmol) of ethanol and 20 ml of n-undecane were charged into an autoclave having an internal volume of 80 ml and reacted at a reaction temperature of 240 ° C. for 7 hours with stirring. After completion of the reaction, the obtained reaction product was analyzed by gas chromatography to find that the naphthalene conversion rate was 32% and the ethylnaphthalene selectivity and yield were 69% and 23%, respectively.
Thus, the proportion of 1-ethyl isomer in the generated etalnaphthalene was 59%.

Comparative Example 1 26.48 g of zirconium oxyhydrochloride octahydrate was dissolved in 200 ml of water, and nitric acid was added to acidify the mixture. While vigorously stirring the solution and maintaining the solution always acidic, a solution prepared by dissolving 32.92 g of an aqueous sodium silicate solution (No. 3) in water to 100 ml was added dropwise. After the dropwise addition of the aqueous sodium silicate solution, ammonia water was added with vigorous stirring for neutralization, the resulting gel was thoroughly washed with water, and then dried at 110 ° C. overnight. Further, the obtained dried gel was calcined at 550 ° C. for 8 hours to obtain a ZrO ₂ —SiO ₂ catalyst having a molar ratio (ZrO ₂ / SiO ₂ ) of 0.5.

2.5 g of the ZrO ₂ —SiO ₂ catalyst thus obtained, 5 g of naphthalene (38.7 mmol), 1.81 g of ethanol (39.2 mmol)
And 20 ml of n-undecane were charged into an 80 ml autoclave and reacted at a reaction temperature of 240 ° C. for 7 hours with stirring. After the reaction was completed, the obtained reaction product was analyzed by gas chromatography, and it was found that the conversion of naphthalene was 60%.
And the selectivity and yield of ethylnaphthalene are 68% each.
And 41%, the ratio of the 2-ethyl compound in the produced etalnaphthalene was 57%.

Comparative Example 2 Sodium silicate aqueous solution (No. 3) 3 in 200 ml of nitric acid aqueous solution
A solution of 2.92 g dissolved in water to 100 ml was added dropwise. At this time, a sufficient amount of nitric acid is added so that the solution is always kept acidic. After the dropwise addition of the aqueous sodium silicate solution, ammonia water was added to the gel while vigorous stirring to neutralize it, and the resulting gel was thoroughly washed with water.

Meanwhile, 26.48 g of zirconium oxyhydrochloride octahydrate was added to water 20
It was dissolved in 0 ml and neutralized by adding aqueous ammonia, the resulting gel was thoroughly washed with water, kneaded with the silica hydrogel prepared above, and dried at 110 ° C. overnight. Further, the obtained dried gel was calcined at 550 ° C. for 8 hours to give Z having a molar ratio (ZrO ₂ / SiO ₂ ) of 0.5.
An rO ₂ —SiO ₂ catalyst was obtained.

2.5 g of the ZrO ₂ —SiO ₂ catalyst thus obtained, 5 g of naphthalene (38.7 mmol), 1.81 g of ethanol (39.2 mmol)
And 20 ml of n-undecane were charged into an 80 ml autoclave and reacted at a reaction temperature of 240 ° C. for 7 hours with stirring. After completion of the reaction, the obtained reaction product was analyzed by gas chromatography and as a result, the conversion of naphthalene was 31%.
And the selectivity and yield of ethylnaphthalene are 93% each.
And 29%, the ratio of the 1-ethyl isomer in the formed etalnaphthalene was 70%.

EFFECTS OF THE INVENTION According to the method of the present invention, there is no problem of acidic waste liquid in the post-treatment after the completion of the reaction, the catalyst is easy to handle and can be reused, and the catalyst is industrially advantageous. It is possible to employ a continuous reaction in a fixed bed flow reaction mode, and since it is a reaction under mild conditions, for example, with a synthetic intermediate such as 2,6-dicarboxylic acid, which is a raw material for producing polyester having excellent physical properties, and the like. The yield and selectivity of the target substance such as 2,6-dialkylnaphthalene can be improved.

Front page continuation (72) Genki Takeuchi Inventor Genki Takeuchi 2-chome Nakai 2-chome, Kokurakita-ku, Kitakyushu, Fukuoka

Claims (4)

(57) [Claims] 1. Periodic table IV obtained by mixing a plurality of kinds of metal compounds in an organic solvent having coordination ability and hydrolyzing them.
An alkyl-substituted aroma characterized by reacting an aromatic compound with an alkylating agent in the presence of a composite metal catalyst having an oxide of a and / or IVb group metal (excluding silica-alumina catalyst). For producing group compounds. 2. A metal of group IVa and IVb of the periodic table is titanium,
The method for producing an alkyl-substituted aromatic compound according to claim 1, which is zirconium or silicon. 3. A periodic table IVa contained in the composite metal catalyst.
3. The method for producing an alkyl-substituted aromatic compound according to claim 1, wherein the metal oxide other than the group IVb metal oxide is an aluminum oxide. 4. A periodic table IV obtained by mixing a plurality of kinds of metal compounds in an organic solvent having a coordinating ability and hydrolyzing them.
A method for producing a 2,6-dialkylnaphthalene, which comprises reacting a 2-alkylnaphthalene with an alkylating agent in the presence of a mixed metal catalyst containing an oxide of a and / or IVb metal.