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WO2014051021A1 - Dialkyl ester de l'acide 1,4-tétralin dicarboxylique et son procédé de production - Google Patents

Dialkyl ester de l'acide 1,4-tétralin dicarboxylique et son procédé de production Download PDF

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Publication number
WO2014051021A1
WO2014051021A1 PCT/JP2013/076199 JP2013076199W WO2014051021A1 WO 2014051021 A1 WO2014051021 A1 WO 2014051021A1 JP 2013076199 W JP2013076199 W JP 2013076199W WO 2014051021 A1 WO2014051021 A1 WO 2014051021A1
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Prior art keywords
dialkyl ester
acid dialkyl
catalyst
mass
dicarboxylic acid
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Japanese (ja)
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WO2014051021A9 (fr
Inventor
阿良加 伊藤
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Mitsubishi Gas Chemical Co Inc
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Mitsubishi Gas Chemical Co Inc
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Priority to JP2014538611A priority Critical patent/JPWO2014051021A1/ja
Publication of WO2014051021A1 publication Critical patent/WO2014051021A1/fr
Publication of WO2014051021A9 publication Critical patent/WO2014051021A9/fr
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/303—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by hydrogenation of unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2602/00—Systems containing two condensed rings
    • C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
    • C07C2602/04—One of the condensed rings being a six-membered aromatic ring
    • C07C2602/10—One of the condensed rings being a six-membered aromatic ring the other ring being six-membered, e.g. tetraline

Definitions

  • 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.
  • 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.
  • naphthalene dicarboxylic acid dialkyl esters 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
  • 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.
  • 1,4-naphthalenedicarboxylic acid dialkyl ester represented by the following formula (2) is hydrogenated to form 1,4-tetralindicarboxylic acid dialkyl ester (hereinafter, “1,4-NDCE”). ), It is necessary to selectively hydrogenate the 5- to 8-positions of the naphthalene ring, but such a hydrogenation method is not yet known.
  • 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.
  • 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.
  • 1,4-tetralin dicarboxylic acid dialkyl ester represented by the 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.
  • 1,4-TDCE which is a novel tetralin derivative
  • 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.
  • 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.
  • the present embodiment 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.
  • a 1,4-tetralin dicarboxylic acid dialkyl ester represented by the formula (1) is provided.
  • R and R ′ represent an alkyl group having 1 to 10 carbon atoms, and R and R ′ may be the same or different.
  • 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.
  • 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.
  • ruthenium 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).
  • 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.
  • 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.
  • 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.
  • 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.
  • a catalyst prepared according to a known method such as an impregnation support method.
  • 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
  • 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)”, “
  • 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.
  • the solvent is not particularly limited as long as it does not inhibit the hydrogenation reaction.
  • 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.
  • 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.
  • 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.
  • 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;
  • 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.
  • 1,4-NDCM dimethyl 1,4-naphthalenedicarboxylate
  • Ru carbon powder A type (5 mass% Ru) / Activated carbon catalyst manufactured by N.E. Chemcat Co., Ltd., water content 52 mass
  • 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).
  • 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.
  • 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.
  • crude 1,4-TDCM dimethyl 1,4-tetralindicarboxylate
  • 1,4-TDCM dimethyl 5,8-tetralindicarboxylate
  • 5 , 8-TDCM dimethyl 5,8-tetralindicarboxylate
  • 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. 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
  • 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.
  • 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.
  • 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).
  • 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.
  • 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.
  • 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), 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).
  • 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.

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PCT/JP2013/076199 2012-09-28 2013-09-27 Dialkyl ester de l'acide 1,4-tétralin dicarboxylique et son procédé de production Ceased WO2014051021A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015059117A (ja) * 2013-09-20 2015-03-30 三菱瓦斯化学株式会社 ２，６−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

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS51100053A (ja) * 1975-01-28 1976-09-03 Hoechst Ag 1*44nafutarinjikarubonsanesuterunoseiho
JPH06157406A (ja) * 1993-04-07 1994-06-03 Mitsui Petrochem Ind Ltd テトラリン誘導体の製造方法
JPH06298919A (ja) * 1993-04-13 1994-10-25 Mitsubishi Rayon Co Ltd ポリエステル製ストレッチフィルム
JPH0753467A (ja) * 1993-08-11 1995-02-28 Teijin Ltd ナフタレンジカルボン酸ジアルキルエステルの水素化方法
WO2013031877A1 (fr) * 2011-09-01 2013-03-07 三菱瓦斯化学株式会社 Composition absorbant l'oxygène et emballage absorbant l'oxygène l'utilisant

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS51100053A (ja) * 1975-01-28 1976-09-03 Hoechst Ag 1*44nafutarinjikarubonsanesuterunoseiho
JPH06157406A (ja) * 1993-04-07 1994-06-03 Mitsui Petrochem Ind Ltd テトラリン誘導体の製造方法
JPH06298919A (ja) * 1993-04-13 1994-10-25 Mitsubishi Rayon Co Ltd ポリエステル製ストレッチフィルム
JPH0753467A (ja) * 1993-08-11 1995-02-28 Teijin Ltd ナフタレンジカルボン酸ジアルキルエステルの水素化方法
WO2013031877A1 (fr) * 2011-09-01 2013-03-07 三菱瓦斯化学株式会社 Composition absorbant l'oxygène et emballage absorbant l'oxygène l'utilisant

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015059117A (ja) * 2013-09-20 2015-03-30 三菱瓦斯化学株式会社 ２，６−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

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