WO2014051021A9

WO2014051021A9 - 1, 4-tetralin dicarboxylic acid dialkyl ester and method for producing same

Info

Publication number: WO2014051021A9
Application number: PCT/JP2013/076199
Authority: WO
Inventors: 阿良加伊藤
Original assignee: 三菱瓦斯化学株式会社
Priority date: 2012-09-28
Filing date: 2013-09-27
Publication date: 2014-08-07
Also published as: JPWO2014051021A1; WO2014051021A1; TW201418211A

Abstract

Provided is a 1, 4-tetralin dicarboxylic acid dialkyl ester represented by formula (1). (In formula (1), R and R' represent C1-10 alkyl groups, and may be identical to or different from one another.)

Description

1,4-Tetraline dicarboxylic acid dialkyl ester and process for producing the same

The present invention relates to a novel tetralin derivative 1,4-tetralin dicarboxylic acid dialkyl ester and a method for producing the same.

Tetraline dicarboxylic acid dialkyl ester has a number of structural isomers depending on the substitution position of the carboxyl group with respect to the tetralin ring. For example,

Patent Documents

1 and 2 disclose 1,5-tetralin dicarboxylic acid dialkyl ester, 1,8-tetralin dicarboxylic acid dialkyl ester, and 2,6-tetralin dicarboxylic acid dialkyl ester. Non-Patent Document 1 discloses 5,8-tetralin dicarboxylic acid dialkyl ester and 5,6-tetralin dicarboxylic acid dialkyl ester.

Patent Documents

1 and 2 disclose a method for producing a dialkyl ester of tetralin dicarboxylic acid by deriving a naphthalene ring into a tetralin ring by hydrogenation of dimethyl naphthalenedicarboxylate. The starting naphthalene dicarboxylic acid dialkyl ester shown in these documents corresponds to one in which one of the two substituents is bonded to the 1 to 4 position of the naphthalene ring and the other to the 5 to 8 position, Moreover, only specific examples are shown in which two substituents are bonded to the 1,5, 1,8 and 2,6 positions of the naphthalene ring. When these naphthalene dicarboxylic acid dialkyl esters are hydrogenated, the same tetralin dicarboxylic acid dimethyl isomer can be obtained regardless of whether the naphthalene ring is hydrogenated at the 1st to 4th or 5th to 8th positions.

JP 2001-278836 A Japanese Patent No. 3210148

[Correction based on Rule 91 23.05.2014]
However, 1,4-tetralindicarboxylic acid dialkyl ester (hereinafter sometimes referred to as “1,4-TDCE”) in which a substituent is bonded to the 1,4-position of the tetralin ring is not limited to any of the above-mentioned documents, etc. Is also not disclosed. Further, a 1,4-naphthalenedicarboxylic acid dialkyl ester (hereinafter sometimes referred to as “1,4-NDCE”) represented by the following formula (2) is hydrogenated to form a 1,4-tetralindicarboxylic acid dialkyl ester. In order to obtain an ester, it is necessary to selectively hydrogenate the 5- to 8-positions of the naphthalene ring, but such a hydrogenation method is not yet known.

On the other hand, if the above-mentioned 1,4-tetralindicarboxylic acid dialkyl ester can be efficiently produced, it can be applied to various uses such as raw materials for various resins, liquid crystal compositions, polymer modifiers, pharmaceutical intermediates and the like. Can be expected well.

The present invention has been made in view of the above circumstances, and is a novel 1 that is considered to be useful as a raw material for resins such as polyester, polycarbonate, polyimide, and polyamide; a liquid crystal composition; a polymer modifier; An object of the present invention is to provide a 1,4-tetralindicarboxylic acid dialkyl ester and a method for producing the same.

As a result of extensive research, the present inventors have surprisingly found that 1,4-TDCE can be synthesized by hydrogenating 1,4-NDCE in a solvent in the presence of a noble metal catalyst. It came to be accomplished.

That is, the present invention is as follows.
[1]
1,4-tetralin dicarboxylic acid dialkyl ester represented by the formula (1).

(In Formula (1), R and R ′ represent an alkyl group having 1 to 10 carbon atoms, and R and R ′ may be the same or different.)
[2]
A process for producing 1,4-tetralindicarboxylic acid dialkyl ester, comprising a step of hydrogenating 1,4-naphthalenedicarboxylic acid dialkyl ester in a solvent in the presence of a noble metal catalyst.
[3]
The method for producing a 1,4-tetralindicarboxylic acid dialkyl ester according to [2], wherein the noble metal catalyst is at least one selected from the group consisting of a ruthenium catalyst, a rhodium catalyst, and a palladium catalyst.
[4]
The method for producing a 1,4-tetralindicarboxylic acid dialkyl ester according to [2], wherein the noble metal catalyst is at least one selected from the group consisting of a ruthenium catalyst and a rhodium catalyst.
[5]
The method for producing a 1,4-tetralindicarboxylic acid dialkyl ester according to any one of [2] to [4], wherein the hydrogenation is performed at a reaction temperature in the range of 0 to 100 ° C.
[6]
The hydrogenation is performed in the presence of a solvent,
The amount of the solvent used is 1,4- according to any one of [2] to [5], which is in a range of 0.5 to 8 in terms of mass ratio to the 1,4-naphthalenedicarboxylic acid dialkyl ester. A method for producing a tetraalkyl dicarboxylic acid dialkyl ester.

According to the present invention, 1,4-TDCE, which is a novel tetralin derivative, can be provided. 1,4-TDCE has great industrial significance because it can be used as a raw material for resins such as polyester, polycarbonate, polyimide, and polyamide, a liquid crystal composition, a polymer modifier, a pharmaceutical intermediate, and the like.

2 is an FT-IR (KBr method) chart of crystals obtained by refining the product of Example 1 by recrystallization. 2 is an FT-IR (KBr method) chart of dimethyl 1,4-naphthalenedicarboxylate used as a raw material in Example 1. FIG. 3 is a result of accurate mass analysis by GC-TOF / MS of a crystal obtained by purifying the product of Example 1 by recrystallization. 1 is a ¹ H-NMR chart of a crystal obtained by purifying the product of Example 1 by recrystallization. 2 is a ¹³ C-NMR chart of a crystal obtained by purifying the product of Example 1 by recrystallization. 2 is a dept135-NMR chart of a crystal obtained by purifying the product of Example 1 by recrystallization. 2 is a ¹³ C-ig-NMR chart of a crystal obtained by purifying the product of Example 1 by recrystallization. 2 is a HMBC-NMR chart of crystals obtained by recrystallizing the product of Example 1. 2 is an HMQC-NMR chart of crystals obtained by purifying the product of Example 1 by recrystallization. 2 is an INADEQUAT-NMR chart of a crystal obtained by purifying the product of Example 1 by recrystallization.

Hereinafter, a mode for carrying out the present invention (hereinafter simply referred to as “the present embodiment”) will be described in detail. The following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents. The present invention can be implemented with appropriate modifications within the scope of the gist thereof.

In this embodiment, a 1,4-tetralin dicarboxylic acid dialkyl ester represented by the formula (1) is provided.

(In Formula (1), R and R ′ represent an alkyl group having 1 to 10 carbon atoms, and R and R ′ may be the same or different.)

In formula (1), R and R ′ each independently represents an alkyl group having 1 to 10 carbon atoms. The alkyl group having 1 to 10 carbon atoms is not particularly limited, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, and an n-heptyl group. Group, n-octyl group, n-nonyl group, n-decyl group and the like.

Among these, from the viewpoint of reactivity when used as a raw material for polyester or polycarbonate, it is preferable that both R and R 'are methyl groups.

The 1,4-tetralin dicarboxylic acid dialkyl ester of the present embodiment includes, for example, 1,4-tetralin dicarboxylic acid dialkyl ester including a step of hydrogenating 1,4-naphthalenedicarboxylic acid dialkyl ester in a solvent in the presence of a noble metal catalyst. It can be obtained by a method for producing an acid dialkyl ester.

Conventionally, it has been difficult to selectively hydrogenate the 5th to 8th positions of 1,4-naphthalenedicarboxylic acid alkyl ester as a raw material. However, as a result of intensive studies by the present inventors, surprisingly, when a hydrogenation reaction is performed in a solvent in the presence of a noble metal catalyst, the 5- to 8-positions of the naphthalene ring can be selectively hydrogenated. It has been found that 1,4-tetralin dicarboxylic acid dialkyl ester is obtained. The reason for this is not clear, but it is usually considered that a ring having two ester groups which are electron-withdrawing substituents is more likely to be hydrogenated electronically, but from the viewpoint of steric hindrance, it has a substituent. Non-rings are more reactive. In this embodiment, as a result of the remarkable influence of steric hindrance, it is unexpectedly estimated that the 5th to 8th positions can be selectively hydrogenated (however, the operation of this embodiment is not limited to this). .)

[1. Catalyst used for reaction]
As the noble metal catalyst, for example, a ruthenium catalyst (Ru), a rhodium catalyst (Rh), a palladium catalyst (Pd), a platinum catalyst (Pt), and an iridium catalyst (Ir) are preferable, and a ruthenium catalyst (Ru) and a rhodium catalyst (Rh). Palladium catalyst (Pd) is more preferable, from the viewpoint of high selectivity in the hydrogenation reaction, ruthenium catalyst and rhodium catalyst are more preferable, and from the viewpoint of higher yield, ruthenium catalyst is still more preferable.

The noble metal catalyst is preferably a catalyst in which a noble metal is supported on a carrier (supported catalyst). Examples of the carrier include carbon, alumina, silica, zeolite, and the like. Among these, carbon such as activated carbon is preferable from the viewpoint of availability and economy. By using the supported catalyst, there are advantages that the amount of catalyst used can be reduced by increasing the surface area, and there are advantages such as availability and safety.

The content of the noble metal in the supported catalyst is preferably 0.1 to 50% by mass, and more preferably 1 to 10% by mass. Specifically, for example, a carbon-supported catalyst containing 0.1 to 50% by mass of the above-mentioned noble metal catalyst, etc., and any one selected from the group consisting of palladium, ruthenium and rhodium is 0.1 to 50% by mass. % Carbon-containing catalyst is more preferable, and a carbon-supported catalyst containing 0.1 to 50% by mass of any one selected from the group consisting of palladium, ruthenium, and rhodium is still more preferable. Further, the catalyst may be dried or hydrated. From the viewpoint of safety and the like, it is preferable to use a water-containing one. The water content in the supported catalyst is preferably 10 to 80% by mass, and more preferably 40 to 60% by mass from the viewpoint of ease of handling.

The above-mentioned catalyst may be a commercially available catalyst or a catalyst prepared according to a known method such as an impregnation support method. For example, “5% Ru carbon powder A type (water-containing product)”, “5% Ru carbon powder B type (water-containing product)”, “5% Ru carbon powder K type (water-containing product)” manufactured by N.E. Ru carbon powder and Ru alumina powder such as “5% Ru carbon powder R type (water-containing product)”, “Ru alumina powder”, “Ru black”; “5% Rh carbon powder (water-containing product)”, “5% Rh carbon powder such as “Rh alumina powder” and Rh alumina powder; “5% Pd carbon powder PE type (hydrated product)”, “5% Pd carbon powder STD type (hydrated product)”, “5% Pd carbon powder K type” (Water-containing product), “5% Pd carbon powder NXA type (water-containing product)”, “5% Pd carbon powder P-type (water-containing product)”, “5% Pd carbon powder AER type (water-containing product)” "5% Pd carbon powder KER type (hydrated product)", "5% Pd carbon powder E type (hydrated product)", "5% Pd carbon powder B type (hydrated product)", "20% Pd carbon powder NX type" (Water-containing product), “20% Pd carbon powder UR type (water-containing product)”, “10% Pd carbon powder NX type (water-containing product)”, “10% Pd carbon powder K type (water-containing product)”, “10% Pd carbon such as “Pd carbon powder PE type (hydrated product)”, “10% Pd carbon powder OH type (hydrated product)”, “10% Pd carbon powder AE type (hydrated product)”, “5% Pd alumina powder”, etc. Examples thereof include powder and Pd alumina powder. As described above, it is of course possible to use a dried product.

The amount of the catalyst used is preferably 0.05 to 5% by mass, more preferably 0.1 to 3% by mass, based on the mass ratio of the noble metal to the raw material 1,4-NDCE. By making the usage-amount of a catalyst into the said range, reaction can be promoted efficiently, suppressing reaction time to a short time, although it is a small usage-amount of a catalyst.

[2. Solvent used for reaction]
The solvent is not particularly limited as long as it does not inhibit the hydrogenation reaction. Examples of the solvent include aliphatic hydrocarbon solvents such as hexane, heptane, octane, nonane, decane, and dodecane, alcohol solvents such as methanol, ethanol, propanol, isopropanol, tert-butanol, ethylene glycol, and glycerin, diethyl ether. , Ether solvents such as tetrahydrofuran, dioxane and the like.

The amount of the solvent used is not particularly limited, but is preferably in the range of 0.5 to 8, more preferably in the range of 0.8 to 5, in terms of mass ratio to 1,4-NDCE. Setting the mass ratio in the above range is preferable because the reaction can be efficiently performed while being easily controlled, and the solvent can be separated and recovered more easily. For example, by setting the mass ratio of the solvent to 1,4-NDCE within the above range, the concentration of the reactant can be increased, so that the reaction efficiency is high and the productivity is excellent. On the other hand, if the concentration is high, the influence of the reaction heat becomes large, and thus the reaction temperature and the like tend to be difficult to control. Reaction control is also easy.

[3. Reaction conditions]
The hydrogenation reaction of this embodiment is usually preferably carried out in a pressurized container such as an autoclave. The pressure of hydrogen in the hydrogenation reaction is not particularly limited, but is preferably 1 to 8 MPa, and more preferably 2 to 5 MPa. By setting the hydrogen pressure within the above range, the position selectivity of the naphthalene ring to the 5th to 8th positions in the hydrogenation reaction is further increased, and 1,4-TDCE can be produced more efficiently.

The reaction temperature of the hydrogenation reaction is usually preferably from 0 to 100 ° C, more preferably from 20 to 70 ° C, still more preferably from 25 to 45 ° C. By performing the hydrogenation reaction in the above temperature range, the regioselectivity of the naphthalene ring to the 5th to 8th positions in the hydrogenation reaction is further increased and the reaction rate is moderate, so that 1,4 is more efficiently performed. -TDCE can be manufactured.

[4. Purification]
After completion of the reaction, for example, the catalyst is filtered off from the reaction mixture, and the filtrate is recovered. If necessary, the catalyst is washed with a solvent having good washing efficiency (extraction efficiency) such as water, acetone, methanol, chloroform, etc., and the washing liquid is recovered. Combine the collected washings with the filtrate to make a mixture. 1,4-TDCE can be taken out by distilling off the solvent from the mixture. Further, purification may be performed by means such as recrystallization, distillation, column chromatography and the like.

The 1,4-tetralindicarboxylic acid dialkyl ester of the present embodiment can be suitably used as a resin raw material such as polyester, polycarbonate, polyimide, polyamide, etc .; liquid crystal composition; polymer modifier;

EXAMPLES The method of the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In the following Examples and Comparative Examples, the composition is based on area percentage values obtained by gas chromatography analysis unless otherwise specified.

<Example 1>
In a 500 mL autoclave (manufactured by SUS316L), 30 g of dimethyl 1,4-naphthalenedicarboxylate (hereinafter referred to as “1,4-NDCM”; manufactured by Wako Pure Chemical Industries, Ltd.), 5% Ru carbon powder A type (5 mass% Ru) / Activated carbon catalyst: manufactured by N.E. Chemcat Co., Ltd., water content 52 mass%) 5.0 g and isopropanol 30 g were charged. At room temperature, the inside of the autoclave was purged with nitrogen twice at a pressure of 1 MPa, and then purged with hydrogen twice at a pressure of 1 MPa. Thereafter, the pressure was reduced to normal pressure, the temperature was raised to 30 ° C., the pressure was increased to 3 MPa with hydrogen, and the mixture was stirred at the same temperature and the same pressure for 2 hours (rotation speed: 500 rpm).
After completion of the reaction, the reaction mixture was cooled to room temperature, hydrogen was released, and the atmosphere was purged with nitrogen twice at a pressure of 1 MPa, and then the catalyst was filtered off to obtain a filtrate. On the other hand, the used catalyst was washed 3 times with 20 g of acetone, and the washing liquid was recovered. The collected washing solution was added to the filtrate to obtain a mixed solution. The solvent was distilled off from the resulting mixture to obtain 29.8 g of crude dimethyl 1,4-tetralindicarboxylate (hereinafter referred to as “crude 1,4-TDCM”). When this was analyzed by gas chromatography, the composition was as follows: 1,4-NDCM: 2.8% by mass, 1,4-TDCM: 87.2% by mass, dimethyl 5,8-tetralindicarboxylate (hereinafter referred to as “5 , 8-TDCM ”): 3.6 mass%. The yield of 1,4-TDCM was 85.2%.
Then, 10 g of acetone and 30 g of decane are added to 10 g of this crude 1,4-TDCM, and after complete dissolution by reflux, the mixture is cooled to 0 ° C. and recrystallized to obtain purified 1,4-TDCM. Released.

FIG. 1 shows an FT-IR (KBr method) chart of the crystals obtained by purifying the product of Example 1 by recrystallization. FIG. 2 shows an FT-IR (KBr method) chart of dimethyl 1,4-naphthalenedicarboxylate used as a raw material in Example 1. FIG. 3 shows the results of accurate mass analysis by GC-TOF / MS of the crystals obtained by purifying the product of Example 1 by recrystallization. FIG. 4 shows a ¹ H-NMR chart of the crystals obtained by purifying the product of Example 1 by recrystallization. FIG. 5 shows a ¹³ C-NMR chart of the crystals obtained by purifying the product of Example 1 by recrystallization. FIG. 6 shows a dept135-NMR chart of the crystals obtained by purifying the product of Example 1 by recrystallization. FIG. 7 shows a ¹³ C-ig-NMR chart of the crystals obtained by purifying the product of Example 1 by recrystallization. FIG. 8 shows an HMBC-NMR chart of the crystals obtained by purifying the product of Example 1 by recrystallization. FIG. 9 shows an HMQC-NMR chart of the crystals obtained by purifying the product of Example 1 by recrystallization. FIG. 10 shows an INADEQUAT-NMR chart of the crystals obtained by purifying the product of Example 1 by recrystallization. The product was identified by the method described later.

<Example 2>
A 500 mL autoclave (manufactured by SUS316L) was charged with 30 g of 1,4-NDCM, 5.0 g of 5% Ru carbon powder A type (manufactured by NE Chemcat Co., Ltd., water content 52 mass%), and 45 g of decane. At room temperature, the inside of the autoclave was purged with nitrogen twice at a pressure of 1 MPa, and then purged with hydrogen twice at a pressure of 1 MPa. Thereafter, the pressure was reduced to normal pressure, the temperature was raised to 40 ° C., the pressure was increased to 3 MPa with hydrogen, and the mixture was stirred at the same temperature and the same pressure for 2 hours (the number of revolutions during stirring was 500 rpm).
After completion of the reaction, the reaction mixture was cooled to room temperature, hydrogen was released, and the atmosphere was purged with nitrogen twice at a pressure of 1 MPa, and then the catalyst was filtered off to obtain a filtrate. On the other hand, the used catalyst was washed 3 times with 20 g of acetone, and the washing liquid was recovered. The collected washing solution was added to the filtrate to obtain a mixed solution. The solvent was distilled off from the resulting mixture to obtain 29.0 g of crude 1,4-TDCM. This was analyzed by gas chromatography. The composition was 1,4-NDCM: 2.6% by mass, 1,4-TDCM: 85.9% by mass, and 5,8-TDCM: 3.5% by mass. It was. The yield of 1,4-TDCM was 81.7%.

<Example 3>
A 500 mL autoclave (manufactured by SUS316L) was charged with 30 g of 1,4-NDCM, 3.0 g of 5% Rh carbon powder (5% by mass Rh / activated carbon catalyst; manufactured by N.E. Chemcat, water content 52% by mass), and 30 g of isopropanol. . At room temperature, the inside of the autoclave was purged with nitrogen twice at a pressure of 1 MPa, and then purged with hydrogen twice at a pressure of 1 MPa. Thereafter, the pressure was reduced to normal pressure, the temperature was raised to 70 ° C., the pressure was increased to 3 MPa with hydrogen, and the mixture was stirred at the same temperature and the same pressure for 2 hours (the number of revolutions during stirring was 500 rpm).
After completion of the reaction, the reaction mixture was cooled to room temperature, hydrogen was released, and the atmosphere was purged with nitrogen twice at 1 MPa, and then the catalyst was filtered off to obtain a filtrate. On the other hand, the used catalyst was washed 3 times with 20 g of acetone, and the washing liquid was recovered. The collected washing solution was added to the filtrate to obtain a mixed solution. The solvent was distilled off from the resulting mixture to obtain 28.8 g of crude 1,4-TDCM. When this was analyzed by gas chromatography, the composition was 1,4-NDCM: 2.0 mass%, 1,4-TDCM: 73.1 mass%, and 5,8-TDCM: 13.7 mass%. It was. The yield of 1,4-TDCM was 69.0%.

<Example 4>
In a 500 mL autoclave (manufactured by SUS316L), 30 g of 1,4-NDCM, 5% Pd carbon powder PE type (5 mass% Pd / activated carbon catalyst; manufactured by N.E. Chemcat, water content 52 mass%), 4.0 g, and isopropanol 100 g Prepared. At room temperature, the inside of the autoclave was purged with nitrogen twice at a pressure of 1 MPa and then purged with hydrogen twice at 1 MPa. Thereafter, the pressure was reduced to normal pressure, the temperature was raised to 90 ° C., the pressure was increased to 3 MPa with hydrogen, and the mixture was stirred at the same temperature and the same pressure for 2 hours (rotation speed: 500 rpm).
After completion of the reaction, the reaction mixture was cooled to room temperature, hydrogen was released, and the atmosphere was purged with nitrogen twice at 1 MPa, and then the catalyst was filtered off to obtain a filtrate. On the other hand, the used catalyst was washed 3 times with 20 g of acetone, and the washing liquid was recovered. The collected washing solution was added to the filtrate to obtain a mixed solution. The solvent was removed from the resulting mixture to obtain 29.9 g of crude 1,4-TDCM. This was analyzed by gas chromatography. The composition was 1,4-NDCM: 0.3% by mass, 1,4-TDCM: 49.8% by mass, and 5,8-TDCM: 47.2% by mass. It was. The yield of 1,4-TDCM was 48.8%.

<Identification of product>
Structure identification was performed on the crystals obtained by recrystallizing the reaction products obtained in each Example. Analysis by FT-IR, NMR, GC-TOF / MS, etc. was performed, and structure identification was performed based on the results.

[FT-IR measurement conditions]
Equipment: “FT-IR410” manufactured by JASCO
Measurement method: Transmission method (KBr method)
Scan range: 500 to 4000 cm ^-1
Integration count: 64
Resolution: 4cm ^-1
Sample preparation: mixed with KBr and molded into tablets.

[NMR measurement conditions]
Apparatus: Bruker Avance II 600MHz-NMR
Probe: DCH CryoProbe
Mode: ¹ H, ¹³ C, ¹³ C-ig, depth 135, HSQC, HMBC, INADEQUATE (measurement time 12 hours)
Sample preparation: 100 mg of crystals were dissolved in 500 μL of deuterated chloroform.

[GC-TOF / MS measurement conditions]
Equipment: Agilent 7890A / Waters GCT Premier
Column: “DB-5MS UI” 30 m × 0.25 mmI. D. Film pressure 0.5μm
Temperature rising conditions: 200 ° C. (0 min) −10 ° C./min−320° C. (0 min)
Split ratio: 1: 100
Inlet temperature: 300 ° C
Amount of implantation: 1.0 μL
Carrier gas: He, 1.0 mL / min
Ionization method: 70 eV, EI + measured mass scan range: 33 to 800 (0.2 sec)
DRE: ON
Trap Current: 200μA
Source temperature: 300 ° C
Interface temperature: 320 ° C
Low Mass Cut OFF: 47 Da
Internal standard substance (mass correction): Heptocasa (m / z = 218.9856)
Sample preparation: Crystals dissolved in chloroform were measured, and data obtained by dilution to a concentration at which the peak intensity was not saturated after measurement was used for accurate mass analysis.

This application is based on a Japanese patent application (Japanese Patent Application No. 2012-216369) filed with the Japan Patent Office on September 28, 2012, the contents of which are incorporated herein by reference.

According to the present invention, 1,4-tetralindicarboxylic acid dialkyl ester, which is a novel tetralin derivative, can be industrially produced by selectively hydrogenating 1,4-naphthalenedicarboxylic acid dialkyl ester. Since 1,4-tetralindicarboxylic acid dialkyl ester can be used as a liquid crystal composition, a polymer modifier, a pharmaceutical intermediate or the like as a polyester, polycarbonate, polyimide, or polyamide, it has great industrial significance.

Claims

1,4-tetralin dicarboxylic acid dialkyl ester represented by the formula (1).

(In Formula (1), R and R ′ represent an alkyl group having 1 to 10 carbon atoms, and R and R ′ may be the same or different.)
A process for producing 1,4-tetralindicarboxylic acid dialkyl ester, comprising a step of hydrogenating 1,4-naphthalenedicarboxylic acid dialkyl ester in a solvent in the presence of a noble metal catalyst.
The method for producing a 1,4-tetralindicarboxylic acid dialkyl ester according to claim 2, wherein the noble metal catalyst is at least one selected from the group consisting of a ruthenium catalyst, a rhodium catalyst, and a palladium catalyst.
The method for producing a 1,4-tetralindicarboxylic acid dialkyl ester according to claim 2, wherein the noble metal catalyst is at least one selected from the group consisting of a ruthenium catalyst and a rhodium catalyst.
The method for producing a 1,4-tetralindicarboxylic acid dialkyl ester according to any one of claims 2 to 4, wherein the hydrogenation is performed in a reaction temperature range of 0 to 100 ° C.
The hydrogenation is performed in the presence of a solvent,
The 1,4-tetralin dicarboxylic acid according to any one of claims 2 to 5, wherein an amount of the solvent used is in a range of 0.5 to 8 in terms of a mass ratio with respect to the 1,4-naphthalenedicarboxylic acid dialkyl ester. Method for producing acid dialkyl ester.