JPWO2014051021A1 - 1,4-Tetralindicarboxylic acid dialkyl ester and process for producing the same - Google Patents

Abstract

Provision of a 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.)

Description

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

  Tetralin dicarboxylic acid dialkyl ester has many 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 raw material naphthalene dicarboxylic acid dialkyl ester shown in these documents corresponds to one in which one of the two substituents is bonded to the 1st to 4th positions of the naphthalene ring and the other to the 5th to 8th positions, 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 is obtained regardless of which of the naphthalene ring is substituted at positions 1-4 or 5-8.

JP 2001-278836 A Japanese Patent No. 3210148

Journal of Organic Chemistry, 1962, 27, p. 5-13

However, 1,4-tetralin dicarboxylic 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. Is also not disclosed. In addition, 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 produced efficiently, 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; , 4-Tetralindicarboxylic acid dialkyl ester, and its manufacturing method are aimed at.

  As a result of diligent 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.

（式（１）中、Ｒ及びＲ’は、炭素数１〜１０のアルキル基を表し、Ｒ及びＲ’は、同一であってもよいし、異なっていてもよい）
〔２〕
１，４−ナフタレンジカルボン酸ジアルキルエステルを、貴金属触媒の存在下、溶媒中で水素添加する工程を含む、１，４−テトラリンジカルボン酸ジアルキルエステルの製造方法。
〔３〕
前記貴金属触媒が、ルテニウム触媒、ロジウム触媒、及びパラジウム触媒からなる群より選ばれる少なくとも１種である、〔２〕に記載の１，４−テトラリンジカルボン酸ジアルキルエステルの製造方法。
〔４〕
前記貴金属触媒が、ルテニウム触媒及びロジウム触媒からなる群より選ばれる少なくとも１種である、〔２〕に記載の１，４−テトラリンジカルボン酸ジアルキルエステルの製造方法。
〔５〕
前記水素添加は、反応温度０〜１００℃の範囲で行われる、〔２〕〜〔４〕のいずれか一項に記載の１，４−テトラリンジカルボン酸ジアルキルエステルの製造方法。
〔６〕
前記水素添加は溶媒存在下で行われ、
前記溶媒の使用量は、前記１，４−ナフタレンジカルボン酸ジアルキルエステルに対する質量比で０．５〜８の範囲である、〔２〕〜〔５〕のいずれか一項に記載の１，４−テトラリンジカルボン酸ジアルキルエステルの製造方法。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 method 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-tetralin dicarboxylic 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 said hydrogenation is a manufacturing method of the 1, 4- tetralin dicarboxylic acid dialkyl ester as described in any one of [2]-[4] performed in the range of reaction temperature 0-100 degreeC.
[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. Since 1,4-TDCE is considered to be used as a resin raw material such as polyester, polycarbonate, polyimide, and polyamide, a liquid crystal composition, a polymer modifier, a pharmaceutical intermediate, and the like, its industrial significance is great.

It is a FT-IR (KBr method) chart of the crystal | crystallization obtained by refine | purifying 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. It is an accurate mass analysis result by GC-TOF / MS of the crystal | crystallization obtained by refine | 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. It is a ¹³ C-NMR chart of the crystal | crystallization obtained by refine | purifying the product of Example 1 by recrystallization. It is a dept135-NMR chart of the crystal | crystallization obtained by refine | purifying the product of Example 1 by recrystallization. It is a ¹³ C-ig-NMR chart of the crystal | crystallization obtained by refine | purifying the product of Example 1 by recrystallization. It is a HMBC-NMR chart of the crystal | crystallization obtained by refine | purifying the product of Example 1 by recrystallization. It is a HMQC-NMR chart of the crystal | crystallization obtained by refine | purifying the product of Example 1 by recrystallization. 2 is an INADEQUAT-NMR chart of crystals 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.

（式（１）中、Ｒ及びＲ’は、炭素数１〜１０のアルキル基を表し、Ｒ及びＲ’は、同一であってもよいし、異なっていてもよい。）In this embodiment, 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. It does not specifically limit as a C1-C10 alkyl group, For example, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl 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 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 5- to 8-positions of the raw material 1,4-naphthalenedicarboxylic acid alkyl ester. However, as a result of diligent research by the present inventors, surprisingly, when a hydrogenation reaction is carried out 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 was found that 1,4-tetralin dicarboxylic acid dialkyl ester was 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-described noble metal catalyst can be used, and any one selected from the group consisting of palladium, ruthenium, and rhodium can be 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 even 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.

  As the catalyst described above, a commercially available catalyst may be used, or a catalyst prepared according to a known method such as an impregnation support method may be used. 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 used amount of the catalyst 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 1,4-NDCE of the raw material. 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.

  Although the usage-amount of a solvent is not specifically limited, It is preferable that it is the range of 0.5-8 by the mass ratio with respect to 1, 4-NDCE, and it is more preferable that it is the range of 0.8-5. 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 hydrogen pressure 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 regioselectivity of the naphthalene ring to the 5- to 8-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 0 to 100 ° C, more preferably 20 to 70 ° C, and still more preferably 25 to 45 ° C. By performing the hydrogenation reaction in the above temperature range, the regioselectivity of the naphthalene ring to the 5- to 8-positions in the hydrogenation reaction is further increased, and the reaction rate is moderate, so that 1,4 is more efficient. -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 mixed solution. Further, purification may be performed by means such as recrystallization, distillation, column chromatography and the like.

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

  The method of the present invention will be described in more detail by way of 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 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% by 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, it is cooled to 0 ° C. and recrystallized, so that purified 1,4-TDCM is simply dissolved. Released.

FIG. 1 shows an FT-IR (KBr method) chart of 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 result of accurate mass analysis by GC-TOF / MS of the crystal obtained by purifying the product of Example 1 by recrystallization. FIG. 4 shows a ¹ H-NMR chart of crystals obtained by purifying the product of Example 1 by recrystallization. FIG. 5 shows a ¹³ C-NMR chart of 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 crystals obtained by refining the product of Example 1 by recrystallization. FIG. 8 shows a 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 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 NP 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. When 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%, 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), 4.0 g of 1,4-NDCM 30 g, 5% Pd carbon powder PE type (5 mass% Pd / activated carbon catalyst; manufactured by N.E. Chemcat, water content 52 mass%), 100 g of isopropanol 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. When 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: 500-4000 cm ⁻¹
Integration count: 64
Resolution: 4cm ^-1
Sample preparation: mixed with KBr and molded into tablets.

[NMR measurement conditions]
Apparatus: Bruker Avance II 600 MHz-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 condition: 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 is considered to be used as a liquid crystal composition, a polymer modifier, a pharmaceutical intermediate, or the like as polyester, polycarbonate, polyimide, or polyamide, its industrial significance is great.

Claims (6)

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 method 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 manufacturing method of the 1, 4- tetralin dicarboxylic acid dialkyl ester of Claim 2 whose said noble metal catalyst is at least 1 sort (s) chosen from the group which consists of a ruthenium catalyst, a rhodium catalyst, and a palladium catalyst.   The method for producing a 1,4-tetralin dicarboxylic 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 said hydrogenation is a manufacturing method of the 1, 4- tetralin dicarboxylic acid dialkyl ester as described in any one of Claims 2-4 performed in the range of reaction temperature 0-100 degreeC. The hydrogenation is performed in the presence of a solvent,
The amount of the solvent used is 1,4-tetralin dicarboxylic acid according to any one of claims 2 to 5, in a mass ratio with respect to the 1,4-naphthalenedicarboxylic acid dialkyl ester of 0.5 to 8. Method for producing acid dialkyl ester.

Images