WO2021153586A1 - METHOD FOR PRODUCING trans, trans-MUCONIC ACID OR ALKYL ESTER THEREOF - Google Patents

METHOD FOR PRODUCING trans, trans-MUCONIC ACID OR ALKYL ESTER THEREOF Download PDF

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WO2021153586A1
WO2021153586A1 PCT/JP2021/002758 JP2021002758W WO2021153586A1 WO 2021153586 A1 WO2021153586 A1 WO 2021153586A1 JP 2021002758 W JP2021002758 W JP 2021002758W WO 2021153586 A1 WO2021153586 A1 WO 2021153586A1
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trans
acid
alkyl ester
reaction
manufactured
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塚本大治郎
河村健司
山田勝成
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東レ株式会社
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/377—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
    • C07C57/02—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
    • C07C57/13—Dicarboxylic acids
    • C07C57/16—Muconic acid
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/297—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups

Definitions

  • the present invention relates to a method for producing trans, trans-muconic acid or an alkyl ester thereof from ⁇ -hydromuconic acid or an alkyl ester thereof.
  • ⁇ -Hydromconic acid also called 2-hexene dicarboxylic acid
  • ⁇ -Hydromconic acid is a 6-carbon dicarboxylic acid having one double bond at the ⁇ -position of the carbonyl carbon.
  • ⁇ -Hydromconic acid can be fermentatively produced by culturing a microorganism capable of producing ⁇ -hydromuconic acid in the presence of a carbon source such as a saccharide derived from biomass (Patent Document 1).
  • the ⁇ -hydromucon acid alkyl ester can be synthesized by esterifying ⁇ -hydromucon acid, and is a polyamide 6 raw material by reacting ⁇ -hydromucon acid or an alkyl ester thereof with hydrogen and ammonia. It can be converted to ⁇ -caprolactam (Patent Document 2).
  • Muconic acid also called 2,4-hexadiene diacid, is a dicarboxylic acid having a conjugated double bond and having 6 carbon atoms. Due to the two double bonds, muconic acid has three geometric isomers, trans, trans-muconic acid, trans, cis-muconic acid, and cis, cis-muconic acid.
  • Trans, trans-muconic acid or an alkyl ester thereof can be converted into terephthalic acid or an alkyl ester thereof, which is a raw material of polyethylene terephthalate or polybutylene terephthalate, by reacting with ethylene and then oxidizing (Patent Document 3).
  • Terephthalic acid is conventionally produced by air-oxidizing para-xylene refined from crude oil.
  • the terephthalic acid alkyl ester is produced by alkyl esterifying terephthalic acid. Therefore, although terephthalic acid and its alkyl esters are all made from fossil resources, there are concerns about future depletion of fossil resources and the problem of global warming due to greenhouse gases emitted by the mining and use of fossil resources. It is desired to establish a method for producing terephthalic acid or an alkyl ester thereof from biomass, which is a renewable resource, or a substance derived from the biomass resource.
  • ⁇ -hydromuconic acid or an alkyl ester thereof can be derived from biomass, and it is known that these can be used as a raw material for ⁇ -caprolactam. Has not been reported. If ⁇ -hydromuconic acid or an alkyl ester thereof can be converted into trans, trans-muconic acid or an alkyl ester thereof, ⁇ -hydromuconic acid or an alkyl ester thereof can be used as a raw material for terephthalic acid or an alkyl ester thereof. Such a method is completely unknown.
  • the present inventor dehydrogenates ⁇ -hydromuconic acid or an alkyl ester thereof in the presence of a dehydrogenation catalyst to cause trans, trans-muconic acid or its alkyl ester. They have found that an alkyl ester can be produced, and have completed the present invention.
  • the present invention is composed of the following (1) to (4).
  • a method for producing trans, trans-muconic acid or an alkyl ester thereof which comprises a step of dehydrogenating ⁇ -hydromuconic acid or an alkyl ester thereof in the presence of a dehydrogenation catalyst.
  • R 1 and R 2 independently represent a hydrogen atom or an alkyl having 1 to 5 carbon atoms, respectively. ].
  • dehydrogenation catalyst is a catalyst containing gold and / or palladium.
  • terephthalic acid or an alkyl ester thereof can be produced from ⁇ -hydromucon acid or an alkyl ester thereof that can be derived from a biomass resource.
  • ⁇ -hydromuconic acid or an alkyl ester thereof is used as a raw material.
  • ⁇ -Hydromconic acid also called 2-hexene dicarboxylic acid
  • 2-hexene dicarboxylic acid is a 6-carbon dicarboxylic acid having one double bond at the ⁇ -position of the carbonyl carbon.
  • the ⁇ -hydromucon acid alkyl ester means a compound in which one or two carboxylic acid groups (-COOH) of ⁇ -hydromucon acid are alkyl ester groups (-COOR).
  • the number of carbon atoms of the alkyl (R) of the alkyl ester group is not particularly limited, and the alkyl (R) may be linear or may have a branched chain.
  • alkyl (R) examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, hepsil, octyl, nonyl, decyl, undecylic, dodecyl, tetradecyl, hexadecyl, eikosyl and the like.
  • a single compound of ⁇ -hydromuconic acid or an alkyl ester thereof may be used as a raw material, or a plurality of mixtures thereof may be used as a raw material.
  • the ⁇ -hydromucon acid or its alkyl ester used in the present invention has a cis form and a trans form due to the presence of a double bond in the molecule, but the ⁇ -hydromucon acid or its alkyl ester in the present invention is cis.
  • the body alone, the trans body alone, or a mixture of the cis body and the trans body may be used as a raw material.
  • the ⁇ -hydromucon acid or an alkyl ester thereof used in the present invention is preferably an ⁇ -hydromucon acid represented by the following general formula (I) or an alkyl ester thereof.
  • R 1 and R 2 independently represent a hydrogen atom or an alkyl having 1 to 5 carbon atoms, respectively.
  • alkyl having 1 to 5 carbon atoms methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, 3-methylbutyl, 1-methylbutyl, 1-ethylpropyl, 1,1 -Dimethylpropyl and 2,2-dimethylpropyl can be exemplified.
  • R 1 and R 2 are independently hydrogen atoms, methyl groups or ethyl groups, respectively, from the viewpoint of availability and availability of raw materials. Is more preferable. Specifically, it is ⁇ -hydromuconic acid represented by the following formulas (I-1) to (I-9) or a monomethyl ester, dimethyl ester, monoethyl ester, diethyl ester, or methyl ethyl ester thereof.
  • ⁇ -hydromucon acid can be fermentatively produced by culturing a microorganism capable of producing ⁇ -hydromucon acid in the presence of a carbon source such as a saccharide that can be derived from biomass. Further, for example, as shown in Scheme 1 below, it can be synthesized from 3-oxoadipic acid.
  • 3-oxoadipic acid can be fermentatively produced by culturing a microorganism capable of producing 3-oxoadipic acid in the presence of a carbon source such as a saccharide derived from a biomass resource (international). Published 2017/099209).
  • ⁇ -hydromuconic acid can also be chemically synthesized from a commercially available reagent based on a method well known to those skilled in the art.
  • the ⁇ -hydromucon acid alkyl ester can be synthesized by esterifying ⁇ -hydromucon acid by a known method. For example, an esterification reaction using an acid catalyst and an alcohol solvent as shown in Reference Example 2 can be mentioned.
  • the acid catalyst used here is not particularly limited, but a mineral acid such as sulfuric acid or hydrochloric acid or a solid acid such as silica or a strongly acidic resin can be used.
  • dehydration condensation of alcohol and carboxylic acid using a condensing agent dehydration condensation of alcohol and carboxylic acid using a Lewis acid catalyst such as boron trifluoride methanol complex, production method under basic conditions using metal alkoxide, and , Methods using alkylating reagents such as diazomethane and alkyl halides.
  • the carboxylic acid (-COOH) of ⁇ -hydromucon acid and ⁇ -hydromucon acid monoester may be either a free form or a salt, and a mixture thereof can be used as a raw material of the present invention.
  • the salt include ammonium salt, lithium salt, sodium salt, potassium salt and the like. Even a mixture of these different salts can be used as a raw material.
  • trans, trans-muconic acid or an alkyl ester thereof can be produced by dehydrogenating ⁇ -hydromuconic acid or an alkyl ester thereof.
  • the trans, trans-muconic acid represented by the following general formula (II) or an alkyl ester thereof can be obtained.
  • R 1 and R 2 which are substituents of the compound represented by the general formula (II), are the same substituents as the raw material compound represented by the general formula (I).
  • trans, trans-muconic acid even if trans, trans-muconic acid alkyl ester produced by dehydrogenation of ⁇ -hydromuconic acid alkyl ester is hydrolyzed to synthesize trans, trans-muconic acid. good. Further, in the case of producing trans, trans-muconic acid alkyl ester, trans, trans-muconic acid alkyl produced by dehydrogenation of ⁇ -hydromuconic acid may be esterified to synthesize trans, trans-muconic acid alkyl ester. good.
  • dehydrogenation of ⁇ -hydromucon acid or an alkyl ester thereof means that ⁇ -hydrogen and ⁇ -hydrogen of ⁇ -hydromucon acid or an alkyl ester thereof are dehydrogenated to form a double bond at the ⁇ -position and the ⁇ -position. It means a reaction in which muconic acid or an alkyl ester thereof is formed.
  • the dehydrogenation catalyst is not particularly limited as long as it has the ability to proceed with the dehydrogenation of ⁇ -hydromuconic acid or an alkyl ester thereof, but hydrocarbons such as ethane, propane, butane, isobutane, butane, ethylbenzene and cyclohexane.
  • hydrocarbons such as ethane, propane, butane, isobutane, butane, ethylbenzene and cyclohexane.
  • a dehydrogenation catalyst used for dehydrogenation of organic compounds such as class, isobutyric acid, methyl isobutyrate, alcohols, cyclohexanone, and tetrahydrocarbazole can be used.
  • chromium oxide (Cr 2 O 3 ), iron oxide (Fe 2 O 3 ), iron phosphate (Fe-P), molybdenum (Mo) heteropolyacid, vanadium phosphate ((VO) 2 P 2 O). 7 ), iridium (Ir), palladium (Pd), platinum (Pt), copper (Cu), gold (Au), a mixture thereof, and the like can be used.
  • a metal containing palladium (Pd) and / or gold (Au) can be preferably used as the dehydrogenation catalyst.
  • the dehydrogenation catalyst one that is dispersed and supported on a carrier can be used from the viewpoint of reduction in the amount used and stability.
  • alumina Al 2 O 3
  • silica-alumina SiO 2- Al 2 O 3
  • silica SiO 2
  • zeolite titania
  • TiO 2 magnesia
  • ZrO 2 zirconia
  • Silica soil carbon (C), hydrotalcite (HT) and the like
  • the amount of the dehydrogenation catalyst supported is not particularly limited, but is usually 0.1 to 20% by weight based on the carrier.
  • the dehydrogenation catalyst can be supported on the carrier by a known method such as an impregnation method, a precipitation precipitation method, or a gas phase supporting method.
  • chromium oxide-supported alumina Cr 2 O 3 / Al 2 O 3
  • palladium-supported alumina Pd / Al 2 O 3
  • platinum-supported alumina Pt / Al 2 O 3
  • Copper-supported alumina Cu / Al 2 O 3
  • gold-supported alumina Au / Al 2 O 3
  • palladium-supported carbon Pd / C
  • platinum-supported carbon Pt / C
  • copper-supported carbon Cu / C
  • Gold-supported carbon Au / C
  • Palladium-supported titania Pd / TiO 2
  • Platinum-supported titania Pt / TiO 2
  • Copper-supported titania Cu / TiO 2
  • Gold-supported titania Au / TiO 2
  • Palladium Supported zirconia Pd / ZrO 2
  • platinum-supported zirconia Pt / Zr
  • Dehydrogenation of ⁇ -hydromuconic acid or its alkyl ester can be carried out in either a gas phase reaction or a liquid phase reaction.
  • reaction type of the gas phase reaction examples include a fixed bed flow type in which the catalyst is allowed to stand, a moving bed flow type in which the catalyst is moved, and a fluid bed flow type in which the catalyst is allowed to flow. Reaction formats are also applicable.
  • the reaction temperature is preferably 200 to 500 ° C., more preferably 250 to 450 ° C., because the raw material does not vaporize when the reaction temperature is lower than the boiling point of the raw material.
  • the pressure in the gas phase reaction is not particularly limited, and the reaction can usually be carried out at atmospheric pressure, but the reaction can be carried out under pressure or reduced pressure with respect to atmospheric pressure.
  • the vaporized raw material can be distributed to the catalyst layer together with the carrier gas.
  • the type of carrier gas is not particularly limited, but air, nitrogen, helium, argon, or a mixed gas thereof is preferably used. Further, the carrier gas may contain water vapor, oxygen and the like.
  • hydrogen gas When hydrogen gas is included, the reverse reaction of the dehydrogenation reaction (hydrogenation reaction) tends to proceed, so it is preferable to carry out the reaction without introducing hydrogen gas.
  • the dehydrogenation catalyst is suspended or filled in a tank-type reactor, and the liquid raw material is brought into contact with the catalyst to carry out the reaction.
  • the reaction form of the liquid phase reaction can be carried out by using any of a batch type tank type reactor, a semi-batch type tank type reactor, a continuous type tank type reactor, and a continuous type tube type reactor. .. Further, in any of the reactors, the reaction can be carried out by any of the suspension bed type, the fixed bed type, the moving bed type and the fluidized bed type.
  • the reaction temperature in the liquid phase reaction is not particularly limited, but is preferably 50 to 300 ° C, more preferably 80 to 280 ° C, and even more preferably 100 to 250 ° C.
  • the pressure in the liquid phase reaction is not particularly limited, but the reaction can be carried out under atmospheric pressure, pressurization, or depressurization.
  • the atmosphere of the liquid phase reaction is not particularly limited, but air, nitrogen, helium, argon, water vapor, oxygen, or a mixed gas thereof may be present.
  • hydrogen gas When hydrogen gas is introduced into the reactor, the reverse reaction of the dehydrogenation reaction (hydrogenation reaction) tends to proceed, so it is preferable to carry out the reaction without introducing hydrogen gas.
  • the dehydrogenation reaction in the liquid phase can be carried out in the presence of a solvent.
  • the solvent is not particularly limited, but it is preferable to use a solvent that is inactive against dehydrogenation, and as such a solvent, water, tert-butanol, 1,2-dimethoxyethane, digrim, dioxane, N-methyl.
  • -2-pyrrolidone, dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide, acetone, acetonitrile, toluene, mesitylene and the like can be mentioned.
  • a solvent having high solubility of ⁇ -hydromuconic acid as a raw material and an alkyl ester thereof and products such as trans, acetone-muconic acid and the alkyl ester thereof is more preferable, and as such a solvent, tert -Butanol, 1,2-dimethoxyethane, digrim, dioxane, N-methyl-2-pyrrolidone, dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide, acetone, acetonitrile and the like can be mentioned.
  • Trans, trans-muconic acid or an alkyl ester thereof produced by dehydrogenation of ⁇ -hydromuconic acid or an alkyl ester thereof can be recovered by ordinary separation and purification operations such as filtration, distillation, extraction and crystallization after the reaction is completed. ..
  • the trans, trans-muconic acid or alkyl ester thereof obtained in the present invention can be converted to terephthalic acid or an alkyl ester thereof by reaction with ethylene and subsequent oxidation (International Publication No. 2010/148801).
  • the terephthalic acid synthesized from trans, trans-muconic acid may be esterified to synthesize a terephthalic acid alkyl ester, or the terephthalic acid alkyl ester synthesized from trans, trans-muconic acid alkyl ester may be hydrolyzed to terephthalic acid. Acids may be synthesized.
  • trans, trans-muconic acid or an alkyl ester thereof to be converted into terephthalic acid or an alkyl ester thereof does not necessarily have to be separated and purified after the dehydrogenation reaction of ⁇ -hydromuconic acid or the alkyl ester thereof.
  • Reaction products containing unpurified trans, trans-muconic acid or alkyl esters thereof may be subjected to conversion to terephthalic acid or alkyl esters thereof.
  • the quantification of the product was performed by gas chromatography (GC) or high performance liquid chromatography (HPLC).
  • GC gas chromatography
  • HPLC high performance liquid chromatography
  • GC analysis conditions GC device: "GC2010 plus” (manufactured by Shimadzu Corporation) Column: “InertCap for amines", length 30 m, inner diameter 0.32 mm (manufactured by GL Science) Carrier gas: helium, constant linear velocity (40.0 cm / sec) Vaporization chamber temperature: 250 ° C Detector temperature: 250 ° C Column oven temperature: 100 ° C ⁇ (10 ° C / min) ⁇ 230 ° C 10 minutes (23 minutes in total) Detector: FID.
  • ⁇ -hydromucon acid (I-1) The ⁇ -hydromucon acid used in the present invention was prepared by chemical synthesis. First, add 1.5 L of ultra-dehydrated tetrahydrofuran (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) to 13.2 g of succinic acid monomethyl ester (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 16.2 g of carbonyldiimidazole (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) with stirring. Wako Pure Chemical Industries, Ltd.
  • trans, trans-dimethyl muconate used as a standard for GC analysis of the product was prepared by chemical synthesis. 1 g of trans, trans-muconic acid (manufactured by Sigma-Aldrich) was dissolved in 10 mL of methanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 2 drops of concentrated sulfuric acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were added. Reflux at 70 ° C. for 6 hours.
  • 5% means that the ratio of palladium to the sum of the weights of palladium and zirconia at the time of raw material preparation is 5% by weight.
  • Gold acid tetrahydrate manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. 0.11 g, palladium chloride (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) 0.005 g, potassium chloride (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) 0 .004 g and 1.2 g of synthetic hydrotalcite (manufactured by Toyama Pharmaceutical Industries, Ltd.) were dissolved in 30 mL of water and stirred overnight. The solid was collected by suction filtration, washed with 500 mL of water, and vacuum dried for 4 hours.
  • Example 1 In a glass reaction vessel with an internal volume of 30 mL, 2.5 mg of ⁇ -hydromuconic acid prepared in Reference Example 1, 2 mL of N, N-dimethylacetamide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 5% palladium as a dehydrogenation catalyst. 5.4 mg of supported carbon (5% Pd / C) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added. In a state of being open to the atmosphere, the temperature was raised to 130 ° C. with stirring at 400 rpm, and the temperature was maintained at 130 ° C. for 30 minutes. Then, it was allowed to cool until it reached room temperature.
  • Example 2 In a glass reaction vessel with an internal volume of 30 mL, 29 mg of dimethyl ⁇ -hydromuconate prepared in Reference Example 2, 10 mL of N, N-dimethylacetamide (DMA, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 5% as a dehydrogenation catalyst. 10 mg of palladium-supported carbon (5% Pd / C) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added. In a state of being open to the atmosphere, the temperature was raised to 130 ° C. while stirring at 600 rpm, and the temperature was maintained at 130 ° C. for 2 hours. Then, it was allowed to cool until it reached room temperature. The supernatant obtained by removing the catalyst by centrifugation was analyzed by GC, and the yields of trans and trans-dimethyl muconate were calculated. The results are shown in Table 1-1.
  • Example 3 Example 2 except that N, N-dimethylformamide (DMF, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was used as the solvent and the gold-palladium-supported hydrotalcite (AuPd / HT) prepared in Reference Example 5 was used as the catalyst. The reaction was carried out in the same manner as in. The results are shown in Table 1-1.
  • DMF N, N-dimethylformamide
  • AuPd / HT gold-palladium-supported hydrotalcite
  • Example 4 The reaction was carried out in the same manner as in Example 3 except that dimethyl sulfoxide (DMSO, manufactured by Wako Pure Chemical Industries, Ltd.) was used as the solvent. The results are shown in Table 1-1.
  • DMSO dimethyl sulfoxide
  • Example 5 The reaction was carried out in the same manner as in Example 3 except that mesitylene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was used as the solvent. The results are shown in Table 1-1.
  • Example 6 The reaction was carried out in the same manner as in Example 3 except that N-methyl-2-pyrrolidone (NMP, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was used as the solvent. The results are shown in Table 1-1.
  • NMP N-methyl-2-pyrrolidone
  • Example 7 In a glass reaction vessel with an internal volume of 30 mL, 29 mg of dimethyl ⁇ -hydromuconate prepared in Reference Example 2, 10 mL of N, N-dimethylacetamide (DMA, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), as a reference example as a dehydrogenation catalyst 20 mg of gold-palladium-supported hydrotalcite (AuPd / HT) prepared in 5 was added. In a state of being open to the atmosphere, the temperature was raised to 130 ° C. while stirring at 600 rpm, and the temperature was maintained at 130 ° C. for 24 hours. Then, it was allowed to cool until it reached room temperature. The supernatant obtained by removing the catalyst by centrifugation was analyzed by GC, and the yields of trans and trans-dimethyl muconate were calculated. The results are shown in Table 1-1.
  • Example 8 The reaction was carried out in the same manner as in Example 7 except that the reaction temperature was set to 150 ° C. The results are shown in Table 1-1.
  • Example 9 The reaction was carried out in the same manner as in Example 7 except that the 5% palladium-supported zirconia (5% Pd / ZrO 2) prepared in Reference Example 4 was used as the catalyst. The results are shown in Table 1-1.
  • Example 10 The reaction was carried out in the same manner as in Example 7 except that 5% palladium-supported alumina (5% Pd / Al 2 O 3) (manufactured by AlphaAesar) was used as the catalyst. The results are shown in Table 1-1.
  • Example 11 The reaction was carried out in the same manner as in Example 7 except that 5% palladium-supported carbon (5% Pd / C) (manufactured by Wako Pure Chemical Industries, Ltd.) was used as the catalyst. The results are shown in Table 1-1.
  • Example 12 The reaction was carried out in the same manner as in Example 7 except that gold-supported hydrotalcite (Au / HT) (manufactured by Wako Pure Chemical Industries, Ltd.) was used as a catalyst. The results are shown in Table 1-1.
  • Example 13 144 mg of dimethyl ⁇ -hydromuconate prepared in Reference Example 2, 50 mL of acetonitrile (MeCN, manufactured by Kokusan Kagaku Co., Ltd.), 5% as a dehydrogenation catalyst in a stainless steel reaction vessel (manufactured by Pressure Resistant Glass Industry Co., Ltd.) with an internal volume of 100 mL. 100 mg of palladium-supported carbon (5% Pd / C) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added.
  • Example 14 The reaction was carried out in the same manner as in Example 13 except that 50 mL of tert-butanol (t-BuOH, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was used as the solvent. The results are shown in Table 1-1.
  • Example 15 The reaction was carried out in the same manner as in Example 13 except that air was introduced instead of nitrogen. The results are shown in Table 1-1.
  • Example 16 The reaction was carried out in the same manner as in Example 15 except that N, N-dimethylacetamide (DMA, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was used as the solvent. The results are shown in Table 1-1.
  • DMA N, N-dimethylacetamide
  • Example 17 The reaction was carried out in the same manner as in Example 13 except that the reaction temperature was set to 250 ° C. The results are shown in Table 1-1.
  • Example 18 In a stainless steel reaction vessel (manufactured by Pressure-Resistant Glass Industry Co., Ltd.) with an internal volume of 100 mL, 144 mg of dimethyl ⁇ -hydromuconate prepared in Reference Example 2 and 30 mL of N, N-dimethylacetamide (DMA, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) , 100 mg of 5% palladium-supported carbon (5% Pd / C) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added as a dehydrogenation catalyst.
  • DMA N, N-dimethylacetamide
  • Example 19 The reaction was carried out in the same manner as in Example 18 except that the reaction temperature was 110 ° C. and the reaction time was 5 hours. The results are shown in Table 1-2.
  • Example 20 The reaction was carried out in the same manner as in Example 18 except that the nitrogen partial pressure was atmospheric pressure, the reaction temperature was 100 ° C., and the reaction time was 13 hours. The results are shown in Table 1-2.
  • Example 21 144 mg of dimethyl ⁇ -hydromuconate prepared in Reference Example 2, 25 mL of acetonitrile (MeCN, manufactured by Kokusan Kagaku Co., Ltd.), 5% as a dehydrogenation catalyst in a stainless steel reaction vessel (manufactured by Pressure Resistant Glass Industry Co., Ltd.) with an internal volume of 100 mL. 100 mg of palladium-supported carbon (5% Pd / C) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added.
  • MeCN acetonitrile
  • 5% palladium-supported carbon
  • Example 22 The reaction was carried out in the same manner as in Example 21 except that 5% palladium-supported alumina (5% Pd / Al 2 O 3) (manufactured by Alfa Aesar) was used as the catalyst. The results are shown in Table 1-2.
  • Example 23 The reaction was carried out in the same manner as in Example 21 except that the reaction temperature was set to 150 ° C. The results are shown in Table 1-2.
  • Example 24 In a glass reaction vessel with an internal volume of 10 mL, 144 mg of dimethyl ⁇ -hydromuconate prepared in Reference Example 2, 3 mL of acetonitrile (MeCN, manufactured by Kokusan Kagaku Co., Ltd.), and 20% palladium-supported carbon (20% Pd /) as a dehydrogenation catalyst. C) 100 mg (manufactured by NT Co., Ltd.) was added. While stirring at a stirring speed of 500 rpm, the temperature inside the reaction vessel was raised to 150 ° C. while nitrogen was flowing through the reaction vessel at a flow rate of 1 mL / min to volatilize the solvent in the reaction vessel. After raising the temperature to 150 ° C.
  • Example 25 The reaction was carried out in the same manner as in Example 13 except that 30 mL of acetonitrile (MeCN, manufactured by Kokusan Kagaku Co., Ltd.) was used and the temperature in the reaction vessel was maintained at 200 ° C. for 3 hours. The results are shown in Table 1-2.
  • Example 26 The reaction was carried out in the same manner as in Example 25 except that the reaction temperature was set to 150 ° C. The results are shown in Table 1-2.
  • trans, trans-muconic acid or an alkyl ester thereof can be produced by dehydrogenating ⁇ -hydromuconic acid or an alkyl ester thereof in the presence of a dehydrogenation catalyst.

Abstract

Trans,trans-muconic acid or an alkyl ester thereof, which serves as a raw material for terephthalic acid or an alkyl ester thereof, is produced by a step in which α-hydromuconic acid or an alkyl ester thereof, which can be derived from biomass resources, is dehydrogenated in the presence of a dehydrogenation catalyst.

Description

ｔｒａｎｓ，ｔｒａｎｓ－ムコン酸又はそのアルキルエステルの製造方法Method for producing trans, trans-muconic acid or an alkyl ester thereof
　本発明は、α－ヒドロムコン酸又はそのアルキルエステルからｔｒａｎｓ，ｔｒａｎｓ－ムコン酸又はそのアルキルエステルを製造する方法に関する。 The present invention relates to a method for producing trans, trans-muconic acid or an alkyl ester thereof from α-hydromuconic acid or an alkyl ester thereof.
　α－ヒドロムコン酸は、２－ヘキセンジカルボン酸とも呼ばれ、カルボニル炭素のα位に二重結合を１つ有する炭素数６のジカルボン酸である。α－ヒドロムコン酸は、バイオマスから誘導可能な糖類等の炭素源の存在下で、α－ヒドロムコン酸生産能を有する微生物を培養することにより、発酵生産することができる（特許文献１）。また、α－ヒドロムコン酸アルキルエステルは、α－ヒドロムコン酸をエステル化することで合成することができ、α－ヒドロムコン酸又はそのアルキルエステルを、水素およびアンモニアと反応させることにより、ポリアミド６原料であるε－カプロラクタムに変換できる（特許文献２）。 Α-Hydromconic acid, also called 2-hexene dicarboxylic acid, is a 6-carbon dicarboxylic acid having one double bond at the α-position of the carbonyl carbon. α-Hydromconic acid can be fermentatively produced by culturing a microorganism capable of producing α-hydromuconic acid in the presence of a carbon source such as a saccharide derived from biomass (Patent Document 1). Further, the α-hydromucon acid alkyl ester can be synthesized by esterifying α-hydromucon acid, and is a polyamide 6 raw material by reacting α-hydromucon acid or an alkyl ester thereof with hydrogen and ammonia. It can be converted to ε-caprolactam (Patent Document 2).
　ムコン酸は、２，４－ヘキサジエン二酸とも呼ばれ、共役二重結合を有する炭素数６のジカルボン酸である。ムコン酸には、その二つの二重結合により、ｔｒａｎｓ，ｔｒａｎｓ－ムコン酸、ｔｒａｎｓ，ｃｉｓ－ムコン酸、ｃｉｓ，ｃｉｓ－ムコン酸の３つの幾何異性体が存在する。ｔｒａｎｓ，ｔｒａｎｓ－ムコン酸又はそのアルキルエステルは、エチレンと反応させてから酸化することにより、ポリエチレンテレフタレートやポリブチレンテレフタレートの原料であるテレフタル酸又はそのアルキルエステルに変換できる（特許文献３）。 Muconic acid, also called 2,4-hexadiene diacid, is a dicarboxylic acid having a conjugated double bond and having 6 carbon atoms. Due to the two double bonds, muconic acid has three geometric isomers, trans, trans-muconic acid, trans, cis-muconic acid, and cis, cis-muconic acid. Trans, trans-muconic acid or an alkyl ester thereof can be converted into terephthalic acid or an alkyl ester thereof, which is a raw material of polyethylene terephthalate or polybutylene terephthalate, by reacting with ethylene and then oxidizing (Patent Document 3).
　テレフタル酸は、従来、原油から精製したパラキシレンを空気酸化することにより製造されている。テレフタル酸アルキルエステルはテレフタル酸をアルキルエステル化することで製造される。したがって、テレフタル酸又はそのアルキルエステルはいずれも化石資源を原料としているが、将来的な化石資源の枯渇懸念や、化石資源の採掘と使用により排出される温室効果ガスによる地球温暖化の問題から、再生可能資源であるバイオマスあるいはバイオマス資源から誘導可能な物質から、テレフタル酸又はそのアルキルエステルを製造する方法の確立が望まれている。 Terephthalic acid is conventionally produced by air-oxidizing para-xylene refined from crude oil. The terephthalic acid alkyl ester is produced by alkyl esterifying terephthalic acid. Therefore, although terephthalic acid and its alkyl esters are all made from fossil resources, there are concerns about future depletion of fossil resources and the problem of global warming due to greenhouse gases emitted by the mining and use of fossil resources. It is desired to establish a method for producing terephthalic acid or an alkyl ester thereof from biomass, which is a renewable resource, or a substance derived from the biomass resource.
国際公開２０１６／１９９８５８号International Publication 2016/199858 国際公開２０１６／０６８１０８号International Publication 2016/068108 国際公開２０１０／１４８０８１号International Release 2010/148801
　上述のように、α－ヒドロムコン酸又はそのアルキルエステルはバイオマスから誘導可能であり、さらに、これらはε－カプロラクタムの原料にできることが知られているが、テレフタル酸又はそのアルキルエステルの原料とする方法は報告されていない。α－ヒドロムコン酸又はそのアルキルエステルをｔｒａｎｓ，ｔｒａｎｓ－ムコン酸又はそのアルキルエステルに変換することができれば、α－ヒドロムコン酸又はそのアルキルエステルをテレフタル酸又はそのアルキルエステルの原料とすることができるが、そのような方法は完全に知られていない。 As mentioned above, α-hydromuconic acid or an alkyl ester thereof can be derived from biomass, and it is known that these can be used as a raw material for ε-caprolactam. Has not been reported. If α-hydromuconic acid or an alkyl ester thereof can be converted into trans, trans-muconic acid or an alkyl ester thereof, α-hydromuconic acid or an alkyl ester thereof can be used as a raw material for terephthalic acid or an alkyl ester thereof. Such a method is completely unknown.
　本発明者は、上記課題を解決するため鋭意研究を行った結果、α－ヒドロムコン酸又はそのアルキルエステルを、脱水素化触媒の存在下、脱水素することにより、ｔｒａｎｓ，ｔｒａｎｓ－ムコン酸又はそのアルキルエステルを製造できることを見出し、本発明を完成するに至った。 As a result of diligent research to solve the above problems, the present inventor dehydrogenates α-hydromuconic acid or an alkyl ester thereof in the presence of a dehydrogenation catalyst to cause trans, trans-muconic acid or its alkyl ester. They have found that an alkyl ester can be produced, and have completed the present invention.
　すなわち、本発明は次の（１）～（４）から構成される。 That is, the present invention is composed of the following (1) to (4).
　（１）α－ヒドロムコン酸又はそのアルキルエステルを、脱水素化触媒の存在下、脱水素化する工程を含む、ｔｒａｎｓ，ｔｒａｎｓ－ムコン酸又はそのアルキルエステルの製造方法。 (1) A method for producing trans, trans-muconic acid or an alkyl ester thereof, which comprises a step of dehydrogenating α-hydromuconic acid or an alkyl ester thereof in the presence of a dehydrogenation catalyst.
　（２）前記α－ヒドロムコン酸又はそのアルキルエステル及び前記ｔｒａｎｓ，ｔｒａｎｓ－ムコン酸又はそのアルキルエステルが、それぞれ以下の一般式（Ｉ）及び（ＩＩ）で示される化合物である、（１）に記載の方法。 (2) The compound according to the following general formulas (I) and (II), wherein the α-hydromuconic acid or an alkyl ester thereof and the trans, trans-muconic acid or an alkyl ester thereof are compounds represented by the following general formulas (I) and (II), respectively. the method of.
Figure JPOXMLDOC01-appb-C000002
Figure JPOXMLDOC01-appb-C000002
［式中、Ｒ１及びＲ２はそれぞれ独立に水素原子又は炭素数１～５のアルキルを表す。］。 [In the formula, R 1 and R 2 independently represent a hydrogen atom or an alkyl having 1 to 5 carbon atoms, respectively. ].
　（３）前記脱水素化する工程が水素ガスを導入しない工程である、（１）又は（２）に記載の方法。 (3) The method according to (1) or (2), wherein the dehydrogenation step is a step in which hydrogen gas is not introduced.
　（４）前記脱水素化触媒が金及び／又はパラジウムを含む触媒である、（１）～（３）のいずれかに記載の方法。 (4) The method according to any one of (1) to (3), wherein the dehydrogenation catalyst is a catalyst containing gold and / or palladium.
　本発明により、バイオマス資源から誘導可能なα－ヒドロムコン酸又はそのアルキルエステルから、テレフタル酸又はそのアルキルエステルを製造することができるようになる。 According to the present invention, terephthalic acid or an alkyl ester thereof can be produced from α-hydromucon acid or an alkyl ester thereof that can be derived from a biomass resource.
　以下、本発明をより詳細に説明する。 Hereinafter, the present invention will be described in more detail.
　［原料］
　本発明では、α－ヒドロムコン酸又はそのアルキルエステルを原料として用いる。 [material]
In the present invention, α-hydromuconic acid or an alkyl ester thereof is used as a raw material.
　α－ヒドロムコン酸は、２－ヘキセンジカルボン酸とも呼ばれ、カルボニル炭素のα位に二重結合を１つ有する炭素数６のジカルボン酸である。 Α-Hydromconic acid, also called 2-hexene dicarboxylic acid, is a 6-carbon dicarboxylic acid having one double bond at the α-position of the carbonyl carbon.
　α－ヒドロムコン酸アルキルエステルとは、α－ヒドロムコン酸の一つ又は二つのカルボン酸基（－ＣＯＯＨ）がアルキルエステル基（－ＣＯＯＲ）である化合物を意味する。アルキルエステル基のアルキル（Ｒ）の炭素数は特に制限されず、また、アルキル（Ｒ）は直鎖であってもよいし、分枝鎖があってもよい。アルキル（Ｒ）の具体例としては、メチル、エチル、プロピル、ブチル、ペンチル、ヘキシル、ヘプシル、オクチル、ノニル、デシル、ウンデシル、ドデシル、テトラデシル、ヘキサデシル、エイコシル等を例示することができる。 The α-hydromucon acid alkyl ester means a compound in which one or two carboxylic acid groups (-COOH) of α-hydromucon acid are alkyl ester groups (-COOR). The number of carbon atoms of the alkyl (R) of the alkyl ester group is not particularly limited, and the alkyl (R) may be linear or may have a branched chain. Specific examples of alkyl (R) include methyl, ethyl, propyl, butyl, pentyl, hexyl, hepsil, octyl, nonyl, decyl, undecylic, dodecyl, tetradecyl, hexadecyl, eikosyl and the like.
　本発明においては、α－ヒドロムコン酸又はそのアルキルエステルのうち、単一の化合物を原料として用いても、複数の混合物を原料として用いてもよい。 In the present invention, a single compound of α-hydromuconic acid or an alkyl ester thereof may be used as a raw material, or a plurality of mixtures thereof may be used as a raw material.
　本発明で用いられるα－ヒドロムコン酸又はそのアルキルエステルには、分子内に二重結合が存在するため、ｃｉｓ体とｔｒａｎｓ体が存在するが、本発明におけるα－ヒドロムコン酸又はそのアルキルエステルはｃｉｓ体単独でもｔｒａｎｓ体単独でも、ｃｉｓ体およびｔｒａｎｓ体の混合物を原料として用いてもよい。 The α-hydromucon acid or its alkyl ester used in the present invention has a cis form and a trans form due to the presence of a double bond in the molecule, but the α-hydromucon acid or its alkyl ester in the present invention is cis. The body alone, the trans body alone, or a mixture of the cis body and the trans body may be used as a raw material.
　本発明で用いられるα－ヒドロムコン酸又はそのアルキルエステルは、以下の一般式（Ｉ）で示されるα－ヒドロムコン酸又はそのアルキルエステルであることが好ましい。一般式（Ｉ）中、Ｒ１及びＲ２はそれぞれ独立に水素原子又は炭素数１～５のアルキルを表す。炭素数１～５のアルキルとしては、メチル、エチル、ｎ－プロピル、イソプロピル、ｎ－ブチル、イソブチル、ｔｅｒｔ－ブチル、ｎ－ペンチル、３－メチルブチル、１－メチルブチル、１－エチルプロピル、１，１－ジメチルプロピル、２，２－ジメチルプロピルを例示することができる。 The α-hydromucon acid or an alkyl ester thereof used in the present invention is preferably an α-hydromucon acid represented by the following general formula (I) or an alkyl ester thereof. In the general formula (I), R 1 and R 2 independently represent a hydrogen atom or an alkyl having 1 to 5 carbon atoms, respectively. As alkyl having 1 to 5 carbon atoms, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, 3-methylbutyl, 1-methylbutyl, 1-ethylpropyl, 1,1 -Dimethylpropyl and 2,2-dimethylpropyl can be exemplified.
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
　本発明で用いられる一般式（Ｉ）で示されるα－ヒドロムコン酸又はそのアルキルエステルは、原料の入手や容易さの観点から、Ｒ１、Ｒ２がそれぞれ独立に水素原子、メチル基又はエチル基であることがより好ましい。具体的には、下記の式（Ｉ－１）から式（Ｉ－９）で示されるα－ヒドロムコン酸又はそのモノメチルエステル、ジメチルエステル、モノエチルエステル、ジエチルエステル、メチルエチルエステルである。 In the α-hydromucon acid represented by the general formula (I) or its alkyl ester used in the present invention, R 1 and R 2 are independently hydrogen atoms, methyl groups or ethyl groups, respectively, from the viewpoint of availability and availability of raw materials. Is more preferable. Specifically, it is α-hydromuconic acid represented by the following formulas (I-1) to (I-9) or a monomethyl ester, dimethyl ester, monoethyl ester, diethyl ester, or methyl ethyl ester thereof.
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
　α－ヒドロムコン酸は、上述のように、バイオマスから誘導可能な糖類等の炭素源の存在下で、α－ヒドロムコン酸生産能を有する微生物を培養することにより、発酵生産することができる。また、例えば、以下のスキーム１に示すように、３－オキソアジピン酸から合成することができる。ここで、３－オキソアジピン酸は、バイオマス資源から誘導された糖類等の炭素源の存在下、３－オキソアジピン酸の生産能を有する微生物を培養することにより、発酵生産することができる（国際公開２０１７／０９９２０９号）。また、α－ヒドロムコン酸は、参考例１に示すように、市販試薬から当業者にとって周知の手法に基づき化学的に合成することもできる。 As described above, α-hydromucon acid can be fermentatively produced by culturing a microorganism capable of producing α-hydromucon acid in the presence of a carbon source such as a saccharide that can be derived from biomass. Further, for example, as shown in Scheme 1 below, it can be synthesized from 3-oxoadipic acid. Here, 3-oxoadipic acid can be fermentatively produced by culturing a microorganism capable of producing 3-oxoadipic acid in the presence of a carbon source such as a saccharide derived from a biomass resource (international). Published 2017/099209). Further, as shown in Reference Example 1, α-hydromuconic acid can also be chemically synthesized from a commercially available reagent based on a method well known to those skilled in the art.
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
　α－ヒドロムコン酸アルキルエステルは、α－ヒドロムコン酸を公知の方法でエステル化することにより合成することができる。例えば、参考例２で示すような酸触媒とアルコール溶媒を用いたエステル化反応が挙げられる。ここで用いる酸触媒は、特に限定されないが、硫酸や塩酸などの鉱酸や、シリカや強酸性樹脂などの固体酸を用いることができる。この他、縮合剤を用いたアルコールとカルボン酸の脱水縮合、三フッ化ホウ素メタノール錯体などのルイス酸触媒を用いたアルコールとカルボン酸の脱水縮合、金属アルコキシドを用いた塩基条件での製造方法や、ジアゾメタンやハロゲン化アルキルなどのアルキル化試薬を用いる方法などが挙げられる。 The α-hydromucon acid alkyl ester can be synthesized by esterifying α-hydromucon acid by a known method. For example, an esterification reaction using an acid catalyst and an alcohol solvent as shown in Reference Example 2 can be mentioned. The acid catalyst used here is not particularly limited, but a mineral acid such as sulfuric acid or hydrochloric acid or a solid acid such as silica or a strongly acidic resin can be used. In addition, dehydration condensation of alcohol and carboxylic acid using a condensing agent, dehydration condensation of alcohol and carboxylic acid using a Lewis acid catalyst such as boron trifluoride methanol complex, production method under basic conditions using metal alkoxide, and , Methods using alkylating reagents such as diazomethane and alkyl halides.
　α－ヒドロムコン酸、α－ヒドロムコン酸モノエステルのカルボン酸（－ＣＯＯＨ）は、フリー体又は塩のいずれであってもよく、これらの混合物であっても本発明の原料として用いることができる。塩としては、例えば、アンモニウム塩、リチウム塩、ナトリウム塩、カリウム塩などが挙げられる。これら異なる塩の混合物であっても原料として使用できる。 The carboxylic acid (-COOH) of α-hydromucon acid and α-hydromucon acid monoester may be either a free form or a salt, and a mixture thereof can be used as a raw material of the present invention. Examples of the salt include ammonium salt, lithium salt, sodium salt, potassium salt and the like. Even a mixture of these different salts can be used as a raw material.
　［生成物］
　本発明では、α－ヒドロムコン酸又はそのアルキルエステルを脱水素化することにより、ｔｒａｎｓ，ｔｒａｎｓ－ムコン酸又はそのアルキルエステルを生成させることができる。具体例として、前記一般式（Ｉ）で示されるα－ヒドロムコン酸又はそのアルキルエステルを脱水素化することで、以下の一般式（ＩＩ）で示されるｔｒａｎｓ，ｔｒａｎｓ－ムコン酸又はそのアルキルエステルを生成させることができる。一般式（ＩＩ）で示される化合物の置換基であるＲ１及びＲ２は、一般式（Ｉ）で示される原料化合物と同じ置換基である。 [Product]
In the present invention, trans, trans-muconic acid or an alkyl ester thereof can be produced by dehydrogenating α-hydromuconic acid or an alkyl ester thereof. As a specific example, by dehydrogenating the α-hydromuconic acid represented by the general formula (I) or an alkyl ester thereof, the trans, trans-muconic acid represented by the following general formula (II) or an alkyl ester thereof can be obtained. Can be generated. R 1 and R 2 , which are substituents of the compound represented by the general formula (II), are the same substituents as the raw material compound represented by the general formula (I).
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
　ｔｒａｎｓ，ｔｒａｎｓ－ムコン酸を製造する場合には、α－ヒドロムコン酸アルキルエステルの脱水素化により生成するｔｒａｎｓ，ｔｒａｎｓ－ムコン酸アルキルエステルを加水分解してｔｒａｎｓ，ｔｒａｎｓ－ムコン酸を合成してもよい。また、ｔｒａｎｓ，ｔｒａｎｓ－ムコン酸アルキルエステルを製造する場合に、α－ヒドロムコン酸の脱水素化により生成するｔｒａｎｓ，ｔｒａｎｓ－ムコン酸をエステル化してｔｒａｎｓ，ｔｒａｎｓ－ムコン酸アルキルエステルを合成してもよい。 In the case of producing trans, trans-muconic acid, even if trans, trans-muconic acid alkyl ester produced by dehydrogenation of α-hydromuconic acid alkyl ester is hydrolyzed to synthesize trans, trans-muconic acid. good. Further, in the case of producing trans, trans-muconic acid alkyl ester, trans, trans-muconic acid alkyl produced by dehydrogenation of α-hydromuconic acid may be esterified to synthesize trans, trans-muconic acid alkyl ester. good.
　α－ヒドロムコン酸又はそのアルキルエステルの脱水素化の過程において、ムコン酸又はそのアルキルエステルのｃｉｓ，ｔｒａｎｓ体、ｃｉｓ，ｃｉｓ体等のｔｒａｎｓ，ｔｒａｎｓ体の幾何異性体が生成した場合には、適宜、これら幾何異性体生成物を異性化反応に供することにより、ｔｒａｎｓ，ｔｒａｎｓ体の収率を向上することができる。ｃｉｓ，ｔｒａｎｓ体、ｃｉｓ，ｃｉｓ体を異性化する方法は特に制限されないが、特許文献３に開示されているようなヨウ素触媒を用いる方法などを適宜用いることができる。 In the process of dehydrogenation of α-hydromuconic acid or its alkyl ester, if geometric isomers of trans, trans isomers such as cis, trans isomers, cis, cis isomers of muconic acid or its alkyl ester are generated, as appropriate. By subjecting these geometric isomer products to an isomerization reaction, the yields of trans and trans isomers can be improved. The method for isomerizing the cis, trans isomer and the cis, cis isomer is not particularly limited, but a method using an iodine catalyst as disclosed in Patent Document 3 can be appropriately used.
　［脱水素化工程］
　本発明において、α－ヒドロムコン酸又はそのアルキルエステルを脱水素化するとは、α－ヒドロムコン酸又はそのアルキルエステルのγ水素、δ水素が脱離することにより、α位とγ位に二重結合を有するムコン酸又はそのアルキルエステルが生成する反応を意味する。 [Dehydrogenation process]
In the present invention, dehydrogenation of α-hydromucon acid or an alkyl ester thereof means that γ-hydrogen and δ-hydrogen of α-hydromucon acid or an alkyl ester thereof are dehydrogenated to form a double bond at the α-position and the γ-position. It means a reaction in which muconic acid or an alkyl ester thereof is formed.
　脱水素化触媒は、α－ヒドロムコン酸又はそのアルキルエステルの脱水素化を進行することができる能力があれば特に制限されないが、エタン、プロパン、ブタン、イソブタン、ブテン、エチルベンゼン、シクロヘキサン等の炭化水素類、イソ酪酸、イソ酪酸メチル、アルコール類、シクロヘキサノン、テトラヒドロカルバゾール等の有機化合物の脱水素化に用いられる脱水素化触媒を用いることができる。具体的には、酸化クロム（Ｃｒ２Ｏ３）、酸化鉄（Ｆｅ２Ｏ３）、リン酸鉄（Ｆｅ－Ｐ）、モリブデン（Ｍｏ）ヘテロポリ酸、リン酸バナジウム（（ＶＯ）２Ｐ２Ｏ７）、イリジウム（Ｉｒ）、パラジウム（Ｐｄ）、白金（Ｐｔ）、銅（Ｃｕ）、金（Ａｕ）、これらの混合物などを用いることができる。脱水素化活性の観点から、パラジウム（Ｐｄ）及び／又は金（Ａｕ）を含む金属を脱水素化触媒として好ましく用いることができる。 The dehydrogenation catalyst is not particularly limited as long as it has the ability to proceed with the dehydrogenation of α-hydromuconic acid or an alkyl ester thereof, but hydrocarbons such as ethane, propane, butane, isobutane, butane, ethylbenzene and cyclohexane. A dehydrogenation catalyst used for dehydrogenation of organic compounds such as class, isobutyric acid, methyl isobutyrate, alcohols, cyclohexanone, and tetrahydrocarbazole can be used. Specifically, chromium oxide (Cr 2 O 3 ), iron oxide (Fe 2 O 3 ), iron phosphate (Fe-P), molybdenum (Mo) heteropolyacid, vanadium phosphate ((VO) 2 P 2 O). 7 ), iridium (Ir), palladium (Pd), platinum (Pt), copper (Cu), gold (Au), a mixture thereof, and the like can be used. From the viewpoint of dehydrogenation activity, a metal containing palladium (Pd) and / or gold (Au) can be preferably used as the dehydrogenation catalyst.
　脱水素化触媒は、使用量の削減や、安定性の観点から担体上に分散担持させたものを使用することができる。担体としては、アルミナ（Ａｌ２Ｏ３）、シリカ－アルミナ（ＳｉＯ２－Ａｌ２Ｏ３）、シリカ（ＳｉＯ２）、ゼオライト、チタニア（ＴｉＯ２）、マグネシア（ＭｇＯ）、ジルコニア（ＺｒＯ２）、珪藻土、炭素（Ｃ）、ハイドロタルサイト（ＨＴ）などを用いることができる。脱水素化触媒の担持量は、特に制限されないが、担体に対して通常０．１～２０重量％である。脱水素化触媒の担体への担持は、含浸法、析出沈殿法、気相担持法など公知の方法により行うことができる。 As the dehydrogenation catalyst, one that is dispersed and supported on a carrier can be used from the viewpoint of reduction in the amount used and stability. As the carrier, alumina (Al 2 O 3 ), silica-alumina (SiO 2- Al 2 O 3 ), silica (SiO 2 ), zeolite, titania (TIO 2 ), magnesia (MgO), zirconia (ZrO 2 ), Silica soil, carbon (C), hydrotalcite (HT) and the like can be used. The amount of the dehydrogenation catalyst supported is not particularly limited, but is usually 0.1 to 20% by weight based on the carrier. The dehydrogenation catalyst can be supported on the carrier by a known method such as an impregnation method, a precipitation precipitation method, or a gas phase supporting method.
　脱水素化触媒と担体の組み合わせとして、酸化クロム担持アルミナ（Ｃｒ２Ｏ３／Ａｌ２Ｏ３）、パラジウム担持アルミナ（Ｐｄ／Ａｌ２Ｏ３）、白金担持アルミナ（Ｐｔ／Ａｌ２Ｏ３）、銅担持アルミナ（Ｃｕ／Ａｌ２Ｏ３）、金担持アルミナ（Ａｕ／Ａｌ２Ｏ３）、パラジウム担持炭素（Ｐｄ／Ｃ）、白金担持炭素（Ｐｔ／Ｃ）、銅担持炭素（Ｃｕ／Ｃ）、金担持炭素（Ａｕ／Ｃ）パラジウム担持チタニア（Ｐｄ／ＴｉＯ２）、白金担持チタニア（Ｐｔ／ＴｉＯ２）、銅担持チタニア（Ｃｕ／ＴｉＯ２）、金担持チタニア（Ａｕ／ＴｉＯ２）、パラジウム担持ジルコニア（Ｐｄ／ＺｒＯ２）、白金担持ジルコニア（Ｐｔ／ＺｒＯ２）、銅担持ジルコニア（Ｃｕ／ＺｒＯ２）、金担持ジルコニア（Ａｕ／ＺｒＯ２）、金担持ハイドロタルサイト（Ａｕ／ＨＴ）、金－パラジウム担持ハイドロタルサイト（ＡｕＰｄ／ＨＴ）を例示することができる。 As a combination of the dehydrogenation catalyst and the carrier, chromium oxide-supported alumina (Cr 2 O 3 / Al 2 O 3 ), palladium-supported alumina (Pd / Al 2 O 3 ), platinum-supported alumina (Pt / Al 2 O 3 ), Copper-supported alumina (Cu / Al 2 O 3 ), gold-supported alumina (Au / Al 2 O 3 ), palladium-supported carbon (Pd / C), platinum-supported carbon (Pt / C), copper-supported carbon (Cu / C) , Gold-supported carbon (Au / C) Palladium-supported titania (Pd / TiO 2 ), Platinum-supported titania (Pt / TiO 2 ), Copper-supported titania (Cu / TiO 2 ), Gold-supported titania (Au / TiO 2 ), Palladium Supported zirconia (Pd / ZrO 2 ), platinum-supported zirconia (Pt / ZrO 2 ), copper-supported zirconia (Cu / ZrO 2 ), gold-supported zirconia (Au / ZrO 2 ), gold-supported hydrotalcite (Au / HT), Gold-palladium-supported hydrotalcite (AuPd / HT) can be exemplified.
　α－ヒドロムコン酸又はそのアルキルエステルの脱水素化は気相反応、液相反応のいずれにおいても実施することができる。 Dehydrogenation of α-hydromuconic acid or its alkyl ester can be carried out in either a gas phase reaction or a liquid phase reaction.
　気相反応では、管型の反応器に脱水素化触媒を充填し、気化させた原料を触媒層に流通させることにより反応を行う。気相反応の反応形式としては、触媒を静置する固定床流通式、触媒を移動させる移動床流通式、触媒を流動させる流動床流通式が挙げられ、本発明の気相反応ではこれらいずれの反応形式も適用できる。 In the gas phase reaction, a tube-type reactor is filled with a dehydrogenation catalyst, and the vaporized raw material is circulated through the catalyst layer to carry out the reaction. Examples of the reaction type of the gas phase reaction include a fixed bed flow type in which the catalyst is allowed to stand, a moving bed flow type in which the catalyst is moved, and a fluid bed flow type in which the catalyst is allowed to flow. Reaction formats are also applicable.
　気相反応では、反応温度が原料の沸点以下であると原料が気化しないため、反応温度は２００～５００℃であることが好ましく、２５０～４５０℃であることがより好ましい。 In the gas phase reaction, the reaction temperature is preferably 200 to 500 ° C., more preferably 250 to 450 ° C., because the raw material does not vaporize when the reaction temperature is lower than the boiling point of the raw material.
　気相反応での圧力は特に制限されず、通常大気圧で反応を行うことができるが、大気圧に対して加圧下、減圧下のいずれにおいても反応を行うことができる。 The pressure in the gas phase reaction is not particularly limited, and the reaction can usually be carried out at atmospheric pressure, but the reaction can be carried out under pressure or reduced pressure with respect to atmospheric pressure.
　気相反応では、気化させた原料をキャリアガスとともに触媒層に流通させることもできる。キャリアガスの種類は特に制限されないが、空気、窒素、ヘリウム、アルゴン、又はこれらの混合気体が好ましく用いられる。また、キャリアガスには水蒸気、酸素等を含ませてもよい。水素ガスを含ませると、脱水素化反応の逆反応（水素化反応）が進行しやすくなるため、水素ガスを導入することなく反応を行うことが好ましい。 In the vapor phase reaction, the vaporized raw material can be distributed to the catalyst layer together with the carrier gas. The type of carrier gas is not particularly limited, but air, nitrogen, helium, argon, or a mixed gas thereof is preferably used. Further, the carrier gas may contain water vapor, oxygen and the like. When hydrogen gas is included, the reverse reaction of the dehydrogenation reaction (hydrogenation reaction) tends to proceed, so it is preferable to carry out the reaction without introducing hydrogen gas.
　液相反応では、槽型の反応器に脱水素化触媒を懸濁あるいは充填し、液状の原料を触媒に接触させることにより反応を行う。液相反応の反応形式は、バッチ式槽型反応器、半バッチ式槽型反応器、連続式槽型反応器、連続式管型反応器のいずれの反応器を用いる形式でも実施することができる。また、いずれの反応器においても、懸濁床式、固定床式、移動床式、流動床式のいずれの方式でも反応を実施することができる。 In the liquid phase reaction, the dehydrogenation catalyst is suspended or filled in a tank-type reactor, and the liquid raw material is brought into contact with the catalyst to carry out the reaction. The reaction form of the liquid phase reaction can be carried out by using any of a batch type tank type reactor, a semi-batch type tank type reactor, a continuous type tank type reactor, and a continuous type tube type reactor. .. Further, in any of the reactors, the reaction can be carried out by any of the suspension bed type, the fixed bed type, the moving bed type and the fluidized bed type.
　液相反応での反応温度は特に制限されないが、５０～３００℃であることが好ましく、８０～２８０℃であることがより好ましく、１００～２５０℃であることがさらに好ましい。 The reaction temperature in the liquid phase reaction is not particularly limited, but is preferably 50 to 300 ° C, more preferably 80 to 280 ° C, and even more preferably 100 to 250 ° C.
　液相反応での圧力は特に制限されないが、大気圧下、加圧下、減圧下のいずれにおいても反応を行うことができる。 The pressure in the liquid phase reaction is not particularly limited, but the reaction can be carried out under atmospheric pressure, pressurization, or depressurization.
　液相反応の雰囲気は特に制限されないが、空気、窒素、ヘリウム、アルゴン、水蒸気、酸素、又はこれらの混合気体が存在していてもよい。水素ガスを反応器に導入すると、脱水素化反応の逆反応（水素化反応）が進行しやすくなるため、水素ガスを導入することなく反応を行うことが好ましい。 The atmosphere of the liquid phase reaction is not particularly limited, but air, nitrogen, helium, argon, water vapor, oxygen, or a mixed gas thereof may be present. When hydrogen gas is introduced into the reactor, the reverse reaction of the dehydrogenation reaction (hydrogenation reaction) tends to proceed, so it is preferable to carry out the reaction without introducing hydrogen gas.
　液相での脱水素化反応は、溶媒存在下で行うことができる。溶媒は特に制限されないが、脱水素化に対して不活性である溶媒を用いることが好ましく、このような溶媒として、水、ｔｅｒｔ－ブタノール、１，２－ジメトキシエタン、ジグリム、ジオキサン、Ｎ－メチル－２－ピロリドン、ジメチルスルホキシド、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、アセトン、アセトニトリル、トルエン、メシチレンなどが挙げられる。また、原料であるα－ヒドロムコン酸及びそのアルキルエステルや、生成物であるｔｒａｎｓ，ｔｒａｎｓ－ムコン酸及びそのアルキルエステルの溶解性が高い溶媒であることがより好ましく、このような溶媒としては、ｔｅｒｔ－ブタノール、１，２－ジメトキシエタン、ジグリム、ジオキサン、Ｎ－メチル－２－ピロリドン、ジメチルスルホキシド、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、アセトン、アセトニトリルなどが挙げられる。 The dehydrogenation reaction in the liquid phase can be carried out in the presence of a solvent. The solvent is not particularly limited, but it is preferable to use a solvent that is inactive against dehydrogenation, and as such a solvent, water, tert-butanol, 1,2-dimethoxyethane, digrim, dioxane, N-methyl. -2-pyrrolidone, dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide, acetone, acetonitrile, toluene, mesitylene and the like can be mentioned. Further, it is more preferable that a solvent having high solubility of α-hydromuconic acid as a raw material and an alkyl ester thereof and products such as trans, acetone-muconic acid and the alkyl ester thereof is more preferable, and as such a solvent, tert -Butanol, 1,2-dimethoxyethane, digrim, dioxane, N-methyl-2-pyrrolidone, dimethyl sulfoxide, N, N-dimethylformamide, N, N-dimethylacetamide, acetone, acetonitrile and the like can be mentioned.
　［ｔｒａｎｓ，ｔｒａｎｓ－ムコン酸又はそのアルキルエステルの回収］
　α－ヒドロムコン酸又はそのアルキルエステルの脱水素化により生成するｔｒａｎｓ，ｔｒａｎｓ－ムコン酸又はそのアルキルエステルは、反応終了後に濾過、蒸留、抽出、晶析など通常の分離精製操作により回収することができる。 [Recovery of trans, trans-muconic acid or its alkyl ester]
Trans, trans-muconic acid or an alkyl ester thereof produced by dehydrogenation of α-hydromuconic acid or an alkyl ester thereof can be recovered by ordinary separation and purification operations such as filtration, distillation, extraction and crystallization after the reaction is completed. ..
　［テレフタル酸又はそのアルキルエステルの製造］
　本発明で得られたｔｒａｎｓ，ｔｒａｎｓ－ムコン酸又はそのアルキルエステルは、エチレンとの反応と、続く、酸化によりテレフタル酸又はそのアルキルエステルに変換できる（国際公開２０１０／１４８０８１号）。この際、ｔｒａｎｓ，ｔｒａｎｓ－ムコン酸から合成したテレフタル酸をエステル化してテレフタル酸アルキルエステルを合成してもよく、ｔｒａｎｓ，ｔｒａｎｓ－ムコン酸アルキルエステルから合成したテレフタル酸アルキルエステルを加水分解してテレフタル酸を合成してもよい。また、テレフタル酸又はそのアルキルエステルへの変換に供するｔｒａｎｓ，ｔｒａｎｓ－ムコン酸又はそのアルキルエステルは、必ずしもα－ヒドロムコン酸又はそのアルキルエステルの脱水素化反応後に分離精製したものである必要はなく、未精製のｔｒａｎｓ，ｔｒａｎｓ－ムコン酸又はそのアルキルエステルを含む反応生成物をテレフタル酸又はそのアルキルエステルへの変換に供してもよい。 [Manufacturing of terephthalic acid or its alkyl ester]
The trans, trans-muconic acid or alkyl ester thereof obtained in the present invention can be converted to terephthalic acid or an alkyl ester thereof by reaction with ethylene and subsequent oxidation (International Publication No. 2010/148801). At this time, the terephthalic acid synthesized from trans, trans-muconic acid may be esterified to synthesize a terephthalic acid alkyl ester, or the terephthalic acid alkyl ester synthesized from trans, trans-muconic acid alkyl ester may be hydrolyzed to terephthalic acid. Acids may be synthesized. Further, the trans, trans-muconic acid or an alkyl ester thereof to be converted into terephthalic acid or an alkyl ester thereof does not necessarily have to be separated and purified after the dehydrogenation reaction of α-hydromuconic acid or the alkyl ester thereof. Reaction products containing unpurified trans, trans-muconic acid or alkyl esters thereof may be subjected to conversion to terephthalic acid or alkyl esters thereof.
　以下、実施例を用いて本発明をより詳細に説明するが、本発明は以下の実施例に限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples.
　生成物の定量は、ガスクロマトグラフィー（ＧＣ）又は高速液体クロマトグラフィー（ＨＰＬＣ）により行った。生成物の定量には、市販標品あるいは化学合成した標品を用いて作成した絶対検量線を用いた。ＧＣ及びＨＰＬＣの分析条件を以下に示す。 The quantification of the product was performed by gas chromatography (GC) or high performance liquid chromatography (HPLC). For the quantification of the product, an absolute calibration curve prepared using a commercially available standard or a chemically synthesized standard was used. The analysis conditions for GC and HPLC are shown below.
　［ＧＣ分析条件］
ＧＣ装置：“ＧＣ２０１０　ｐｌｕｓ”（株式会社島津製作所製）
カラム：“ＩｎｅｒｔＣａｐ　ｆｏｒ　ａｍｉｎｅｓ”、長さ３０ｍ、内径０．３２ｍｍ（ＧＬサイエンス社製）
キャリアガス：ヘリウム、線速度一定（４０．０ｃｍ／秒）
気化室温度：２５０℃
検出器温度：２５０℃
カラムオーブン温度：１００℃→（１０℃／分）→２３０℃　１０分（計２３分）
検出器：ＦＩＤ。 [GC analysis conditions]
GC device: "GC2010 plus" (manufactured by Shimadzu Corporation)
Column: "InertCap for amines", length 30 m, inner diameter 0.32 mm (manufactured by GL Science)
Carrier gas: helium, constant linear velocity (40.0 cm / sec)
Vaporization chamber temperature: 250 ° C
Detector temperature: 250 ° C
Column oven temperature: 100 ° C → (10 ° C / min) → 230 ° C 10 minutes (23 minutes in total)
Detector: FID.
　［ＨＰＬＣ分析条件］
ＨＰＬＣ装置：Ｐｒｏｍｉｎｅｎｃｅ（株式会社島津製作所社製）
カラム：Ｓｙｎｅｒｇｉ　ｈｙｄｒｏ－ＲＰ（Ｐｈｅｎｏｍｅｎｅｘ社製）、長さ２５０ｍｍ、内径４．６０ｍｍ、粒径４μｍ
移動相：０．１重量％リン酸水溶液／アセトニトリル＝９５／５（体積比）  
流速：１．０ｍＬ／分
検出器：ＵＶ（２１０ｎｍ）
カラム温度：４０℃。 [HPLC analysis conditions]
HPLC device: Prominence (manufactured by Shimadzu Corporation)
Column: Synergy hydro-RP (manufactured by Phenomenex), length 250 mm, inner diameter 4.60 mm, particle size 4 μm
Mobile phase: 0.1 wt% aqueous phosphoric acid solution / acetonitrile = 95/5 (volume ratio)
Flow velocity: 1.0 mL / min Detector: UV (210 nm)
Column temperature: 40 ° C.
　（参考例１）α－ヒドロムコン酸（Ｉ－１）の調製
　本発明で使用したα－ヒドロムコン酸は化学合成により調製した。まず、コハク酸モノメチルエステル１３．２ｇ（富士フイルム和光純薬株式会社製）に超脱水テトラヒドロフラン１．５Ｌ（富士フイルム和光純薬株式会社製）を加え、攪拌しながらカルボニルジイミダゾール１６．２ｇ（富士フイルム和光純薬株式会社製）を添加し、窒素雰囲気下１時間室温で攪拌した。この懸濁液にマロン酸モノメチルエステルカリウム塩１５．６ｇ及び塩化マグネシウム９．５ｇを添加し、窒素雰囲気下１時間室温で攪拌した後、４０℃で１２時間攪拌した。反応終了後、１ｍｏｌ／Ｌ塩酸を０．０５Ｌ加え、酢酸エチルにより抽出し、シリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝１：５）で分離精製することで、純粋な３－オキソヘキサンジカルボン酸ジメチルエステル１３．１ｇを得た。 (Reference Example 1) Preparation of α-hydromucon acid (I-1) The α-hydromucon acid used in the present invention was prepared by chemical synthesis. First, add 1.5 L of ultra-dehydrated tetrahydrofuran (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) to 13.2 g of succinic acid monomethyl ester (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 16.2 g of carbonyldiimidazole (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) with stirring. Wako Pure Chemical Industries, Ltd. (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was stirred at room temperature for 1 hour in a nitrogen atmosphere. To this suspension, 15.6 g of potassium malonic acid monomethyl ester and 9.5 g of magnesium chloride were added, and the mixture was stirred under a nitrogen atmosphere for 1 hour at room temperature and then at 40 ° C. for 12 hours. After completion of the reaction, 0.05 L of 1 mol / L hydrochloric acid was added, the mixture was extracted with ethyl acetate, and separated and purified by silica gel column chromatography (hexane: ethyl acetate = 1: 5) to obtain pure dimethyl 3-oxohexanedicarboxylate. 13.1 g of ester was obtained.
　得られた３－オキソヘキサンジカルボン酸ジメチルエステル１０ｇにメタノール０．１Ｌ（国産化学株式会社製）を加え、攪拌しながら水素化ホウ素ナトリウム２．０ｇ（富士フイルム和光純薬株式会社製）を添加し、室温で１時間攪拌した。次いで、５ｍｏｌ／Ｌの水酸化ナトリウム水溶液０．０２Ｌを添加し、室温で２時間攪拌した。反応終了後、５ｍｏｌ／Ｌの塩酸でｐＨ１に調整し、ロータリーエバポレーターで濃縮後、水で再結晶することで、純粋なα－ヒドロムコン酸７．２ｇを得た。得られたα－ヒドロムコン酸のＮＭＲスペクトルは以下の通り。 To 10 g of the obtained 3-oxohexanedicarboxylic acid dimethyl ester, 0.1 L of methanol (manufactured by Kokusan Kagaku Co., Ltd.) was added, and 2.0 g of sodium borohydride (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added with stirring. , Stirred at room temperature for 1 hour. Then, 0.02 L of a 5 mol / L sodium hydroxide aqueous solution was added, and the mixture was stirred at room temperature for 2 hours. After completion of the reaction, the pH was adjusted to 1 with 5 mol / L hydrochloric acid, concentrated with a rotary evaporator, and recrystallized from water to obtain 7.2 g of pure α-hydromuconic acid. The NMR spectrum of the obtained α-hydromucon acid is as follows.
　１Ｈ－ＮＭＲ（４００ＭＨｚ、ＣＤ３ＯＤ）：δ２．４８（ｍ、４Ｈ）、δ５．８４（ｄ、１Ｈ）、δ６．９６（ｍ、１Ｈ）。 1 1 H-NMR (400 MHz, CD 3 OD): δ2.48 (m, 4H), δ5.84 (d, 1H), δ6.96 (m, 1H).
　（参考例２）α－ヒドロムコン酸ジメチル（Ｉ－４）の調製
　本発明で使用したα－ヒドロムコン酸ジメチルは化学合成により調製した。参考例１で調製したα－ヒドロムコン酸１ｇをメタノール１０ｍＬ（富士フイルム和光純薬工業株式会社製）に溶かし、濃硫酸（富士フイルム和光純薬工業株式会社製）２滴を添加し、７０℃で６時間還流した。反応終了後、ロータリーエバポレーターで濃縮し、シリカゲルカラムクロマトグラフィー（ヘキサン：酢酸エチル＝７：３）で精製することで、純粋なα－ヒドロムコン酸ジメチル０．９ｇを得た。得られたα－ヒドロムコン酸ジメチルのＮＭＲスペクトルは以下の通り。 (Reference Example 2) Preparation of dimethyl α-hydromuconate (I-4) The dimethyl α-hydromuconate used in the present invention was prepared by chemical synthesis. Dissolve 1 g of α-hydromuconic acid prepared in Reference Example 1 in 10 mL of methanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), add 2 drops of concentrated sulfuric acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and at 70 ° C. Refluxed for 6 hours. After completion of the reaction, the mixture was concentrated on a rotary evaporator and purified by silica gel column chromatography (hexane: ethyl acetate = 7: 3) to obtain 0.9 g of pure dimethyl α-hydromuconate. The NMR spectrum of the obtained dimethyl α-hydromuconate is as follows.
　１Ｈ－ＮＭＲ（４００ＭＨｚ、ＣＤＣｌ３）：δ２．４６－２．５７（ｍ、４Ｈ）、δ３．６９（ｓ、３Ｈ）、δ３．７３（ｓ、３Ｈ）、δ５．８６（ｄ、１Ｈ）、δ６．９５（ｄｔ、１Ｈ）。 1 1 H-NMR (400 MHz, CDCl 3 ): δ2.46-2.57 (m, 4H), δ3.69 (s, 3H), δ3.73 (s, 3H), δ5.86 (d, 1H) , Δ6.95 (dt, 1H).
　（参考例３）ｔｒａｎｓ，ｔｒａｎｓ－ムコン酸ジメチルの調製
　生成物のＧＣ分析の標品に用いたｔｒａｎｓ，ｔｒａｎｓ－ムコン酸ジメチルは化学合成により準備した。ｔｒａｎｓ，ｔｒａｎｓ－ムコン酸１ｇ（シグマ－アルドリッチ社製）をメタノール１０ｍＬ（富士フイルム和光純薬工業株式会社製）に溶かし、濃硫酸２滴（富士フイルム和光純薬工業株式会社製）を添加し、７０℃で６時間還流した。反応終了後、ロータリーエバポレーターで濃縮後、メタノールで再結晶することで、純粋なｔｒａｎｓ，ｔｒａｎｓ－ムコン酸ジメチル０．８ｇを得た。得られたｔｒａｎｓ，ｔｒａｎｓ－ムコン酸ジメチルのＮＭＲスペクトルは以下の通り。 (Reference Example 3) Preparation of trans, trans-dimethyl muconate The trans, trans-dimethyl muconate used as a standard for GC analysis of the product was prepared by chemical synthesis. 1 g of trans, trans-muconic acid (manufactured by Sigma-Aldrich) was dissolved in 10 mL of methanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 2 drops of concentrated sulfuric acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were added. Reflux at 70 ° C. for 6 hours. After completion of the reaction, the mixture was concentrated with a rotary evaporator and recrystallized from methanol to obtain 0.8 g of pure trans, trans-muconate dimethyl. The NMR spectra of the obtained trans and trans-dimethyl muconate are as follows.
　１Ｈ－ＮＭＲ（４００ＭＨｚ、ＣＤＣｌ３）：δ３．７６（ｓ、６Ｈ）、δ６．３２（ｄ、２Ｈ）、δ７．３８（ｄ、２Ｈ）。 1 1 H-NMR (400 MHz, CDCl 3 ): δ3.76 (s, 6H), δ6.32 (d, 2H), δ7.38 (d, 2H).
　（参考例４）５％パラジウム担持ジルコニア（５％Ｐｄ／ＺｒＯ２）の準備
　硝酸パラジウム（Ｐｄ（ＮＯ３）２・２Ｈ２Ｏ、Ａｌｆａ　Ａｅｓａｒ社製）０．１３ｇを水１０ｍＬに溶解した水溶液に、ジルコニア（ＺｒＯ２、ＪＲＣ－ＺＲＯ－３、触媒学会参照触媒）１ｇを添加し、室温で３時間撹拌した。ロータリーエバポレーターを用いて２０ｍｍＨｇ、４０℃で水分を蒸発させ、得られた粉末を１１０℃で一晩乾燥したのち、空気流通下、５００℃で４時間焼成した。続いて該粉末を、水素流通下、４００℃で２時間処理することにより、５％パラジウム担持ジルコニア（５％Ｐｄ／ＺｒＯ２）を得た。ここで５％とは、原料仕込み時において、パラジウムとジルコニアの重量の和に対するパラジウムの割合が５重量％であることを意味する。 (Reference Example 4) Preparation of palladium nitrate in 5% palladium on zirconia (5% Pd / ZrO 2) (Pd (NO 3) 2 · 2H 2 O, Alfa Aesar Co., Ltd.) 0.13g aqueous solution dissolved in water 10mL , Zirconia (ZrO 2 , JRC-ZRO-3, catalyst referenced by the Society of Catalysis) was added, and the mixture was stirred at room temperature for 3 hours. Moisture was evaporated at 20 mmHg and 40 ° C. using a rotary evaporator, and the obtained powder was dried at 110 ° C. overnight and then calcined at 500 ° C. for 4 hours under air circulation. Subsequently, the powder was treated at 400 ° C. for 2 hours under hydrogen flow to obtain 5% palladium-supported zirconia (5% Pd / ZrO 2 ). Here, 5% means that the ratio of palladium to the sum of the weights of palladium and zirconia at the time of raw material preparation is 5% by weight.
　（参考例５）金－パラジウム担持ハイドロタルサイト（ＡｕＰｄ／ＨＴ）の準備
　触媒の調製は、「Ｃｈｅｍｉｃａｌ　Ｓｃｉｅｎｃｅ，ｖｏｌ．７，ｐ５３７１－５３８３（２０１６）」を参考とした。塩化金酸四水和物（富士フイルム和光純薬株式会社製）０．１１ｇ、塩化パラジウム（富士フイルム和光純薬株式会社製）０．００５ｇ、塩化カリウム（富士フイルム和光純薬株式会社製）０．００４ｇ、合成ハイドロタルサイト（富山製薬株式会社製）１．２ｇを水３０ｍＬに溶解させ、一晩撹拌した。吸引ろ過により固体を回収し、水５００ｍＬで洗浄してから４時間真空乾燥した。得られた粉末０．４ｇを８ｍＬの水に懸濁させ、水２ｍＬに溶解させた水素化ホウ素ナトリウム１６．８ｍｇを滴下した。吸引ろ過により粉末を回収し、水５００ｍＬで洗浄してから４時間真空乾燥し、深い灰色の金－パラジウム担持ハイドロタルサイト（ＡｕＰｄ／ＨＴ）０．３８ｇを得た。 (Reference Example 5) Preparation of Gold-Palladium-Supported Hydrotalcite (AuPd / HT) For the preparation of the catalyst, "Chemical Science, vol.7, p5371-5383 (2016)" was referred to. Gold acid tetrahydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) 0.11 g, palladium chloride (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) 0.005 g, potassium chloride (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) 0 .004 g and 1.2 g of synthetic hydrotalcite (manufactured by Toyama Pharmaceutical Industries, Ltd.) were dissolved in 30 mL of water and stirred overnight. The solid was collected by suction filtration, washed with 500 mL of water, and vacuum dried for 4 hours. 0.4 g of the obtained powder was suspended in 8 mL of water, and 16.8 mg of sodium borohydride dissolved in 2 mL of water was added dropwise. The powder was collected by suction filtration, washed with 500 mL of water, and vacuum dried for 4 hours to obtain 0.38 g of deep gray gold-palladium-supported hydrotalcite (AuPd / HT).
　（実施例１）
　内容量３０ｍＬのガラス製反応容器に、参考例１で調製したα－ヒドロムコン酸２．５ｍｇ、Ｎ，Ｎ－ジメチルアセトアミド２ｍＬ（富士フイルム和光純薬株式会社製）、脱水素化触媒として５％パラジウム担持炭素（５％Ｐｄ／Ｃ）５．４ｍｇ（富士フイルム和光純薬株式会社製）を添加した。大気に開放した状態で、４００ｒｐｍで撹拌しながら１３０℃まで昇温し、３０分間１３０℃で保持した。その後、室温になるまで放冷した。水を加えて２０ｍＬにメスアップした水溶液から遠心分離により触媒を除去して得た上清をＨＰＬＣにより分析し、ｔｒａｎｓ，ｔｒａｎｓ－ムコン酸の収量を算出した。結果を表１－１に示す。 (Example 1)
In a glass reaction vessel with an internal volume of 30 mL, 2.5 mg of α-hydromuconic acid prepared in Reference Example 1, 2 mL of N, N-dimethylacetamide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 5% palladium as a dehydrogenation catalyst. 5.4 mg of supported carbon (5% Pd / C) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added. In a state of being open to the atmosphere, the temperature was raised to 130 ° C. with stirring at 400 rpm, and the temperature was maintained at 130 ° C. for 30 minutes. Then, it was allowed to cool until it reached room temperature. The supernatant obtained by removing the catalyst by centrifugation from the aqueous solution prepared by adding water to 20 mL was analyzed by HPLC, and the yields of trans and trans-muconic acid were calculated. The results are shown in Table 1-1.
　（実施例２）
　内容量３０ｍＬのガラス製反応容器に、参考例２で調製したα－ヒドロムコン酸ジメチル２９ｍｇ、Ｎ，Ｎ－ジメチルアセトアミド１０ｍＬ（ＤＭＡ、富士フイルム和光純薬株式会社製）、脱水素化触媒として５％パラジウム担持炭素（５％Ｐｄ／Ｃ）１０ｍｇ（富士フイルム和光純薬株式会社製）を添加した。大気に開放した状態で、６００ｒｐｍで撹拌しながら１３０℃まで昇温し、２時間１３０℃で保持した。その後、室温になるまで放冷した。遠心分離により触媒を除去して得た上清をＧＣにより分析し、ｔｒａｎｓ，ｔｒａｎｓ－ムコン酸ジメチルの収量を算出した。結果を表１－１に示す。 (Example 2)
In a glass reaction vessel with an internal volume of 30 mL, 29 mg of dimethyl α-hydromuconate prepared in Reference Example 2, 10 mL of N, N-dimethylacetamide (DMA, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 5% as a dehydrogenation catalyst. 10 mg of palladium-supported carbon (5% Pd / C) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added. In a state of being open to the atmosphere, the temperature was raised to 130 ° C. while stirring at 600 rpm, and the temperature was maintained at 130 ° C. for 2 hours. Then, it was allowed to cool until it reached room temperature. The supernatant obtained by removing the catalyst by centrifugation was analyzed by GC, and the yields of trans and trans-dimethyl muconate were calculated. The results are shown in Table 1-1.
　（実施例３）
　溶媒にＮ，Ｎ－ジメチルホルムアミド（ＤＭＦ、富士フイルム和光純薬株式会社製）、触媒に参考例５で調製した金－パラジウム担持ハイドロタルサイト（ＡｕＰｄ／ＨＴ）を用いた以外は、実施例２と同様に反応を行った。結果を表１－１に示す。 (Example 3)
Example 2 except that N, N-dimethylformamide (DMF, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was used as the solvent and the gold-palladium-supported hydrotalcite (AuPd / HT) prepared in Reference Example 5 was used as the catalyst. The reaction was carried out in the same manner as in. The results are shown in Table 1-1.
　（実施例４）
　溶媒にジメチルスルホキシド（ＤＭＳＯ、富士フイルム和光純薬株式会社製）を用いた以外は、実施例３と同様に反応を行った。結果を表１－１に示す。 (Example 4)
The reaction was carried out in the same manner as in Example 3 except that dimethyl sulfoxide (DMSO, manufactured by Wako Pure Chemical Industries, Ltd.) was used as the solvent. The results are shown in Table 1-1.
　（実施例５）
　溶媒にメシチレン（富士フイルム和光純薬株式会社製）を用いた以外は、実施例３と同様に反応を行った。結果を表１－１に示す。 (Example 5)
The reaction was carried out in the same manner as in Example 3 except that mesitylene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was used as the solvent. The results are shown in Table 1-1.
　（実施例６）
　溶媒にＮ－メチル－２－ピロリドン（ＮＭＰ、富士フイルム和光純薬株式会社製）を用いた以外は、実施例３と同様に反応を行った。結果を表１－１に示す。 (Example 6)
The reaction was carried out in the same manner as in Example 3 except that N-methyl-2-pyrrolidone (NMP, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was used as the solvent. The results are shown in Table 1-1.
　（実施例７）
　内容量３０ｍＬのガラス製反応容器に、参考例２で調製したα－ヒドロムコン酸ジメチル２９ｍｇ、Ｎ，Ｎ－ジメチルアセトアミド１０ｍＬ（ＤＭＡ、富士フイルム和光純薬株式会社製）、脱水素化触媒として参考例５で調製した金－パラジウム担持ハイドロタルサイト（ＡｕＰｄ／ＨＴ）２０ｍｇを添加した。大気に開放した状態で、６００ｒｐｍで撹拌しながら１３０℃まで昇温し、２４時間１３０℃で保持した。その後、室温になるまで放冷した。遠心分離により触媒を除去して得た上清をＧＣにより分析し、ｔｒａｎｓ，ｔｒａｎｓ－ムコン酸ジメチルの収量を算出した。結果を表１－１に示す。 (Example 7)
In a glass reaction vessel with an internal volume of 30 mL, 29 mg of dimethyl α-hydromuconate prepared in Reference Example 2, 10 mL of N, N-dimethylacetamide (DMA, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), as a reference example as a dehydrogenation catalyst 20 mg of gold-palladium-supported hydrotalcite (AuPd / HT) prepared in 5 was added. In a state of being open to the atmosphere, the temperature was raised to 130 ° C. while stirring at 600 rpm, and the temperature was maintained at 130 ° C. for 24 hours. Then, it was allowed to cool until it reached room temperature. The supernatant obtained by removing the catalyst by centrifugation was analyzed by GC, and the yields of trans and trans-dimethyl muconate were calculated. The results are shown in Table 1-1.
　（実施例８）
　反応温度を１５０℃にした以外は、実施例７と同様に反応を行った。結果を表１－１に示す。 (Example 8)
The reaction was carried out in the same manner as in Example 7 except that the reaction temperature was set to 150 ° C. The results are shown in Table 1-1.
　（実施例９）
　触媒に参考例４で調製した５％パラジウム担持ジルコニア（５％Ｐｄ／ＺｒＯ２）を用いた以外は、実施例７と同様に反応を行った。結果を表１－１に示す。 (Example 9)
The reaction was carried out in the same manner as in Example 7 except that the 5% palladium-supported zirconia (5% Pd / ZrO 2) prepared in Reference Example 4 was used as the catalyst. The results are shown in Table 1-1.
　（実施例１０）
　触媒に５％パラジウム担持アルミナ（５％Ｐｄ／Ａｌ２Ｏ３）（ＡｌｆａＡｅｓａｒ社製）を用いた以外は、実施例７と同様に反応を行った。結果を表１－１に示す。 (Example 10)
The reaction was carried out in the same manner as in Example 7 except that 5% palladium-supported alumina (5% Pd / Al 2 O 3) (manufactured by AlphaAesar) was used as the catalyst. The results are shown in Table 1-1.
　（実施例１１）
　触媒に５％パラジウム担持炭素（５％Ｐｄ／Ｃ）（富士フイルム和光純薬株式会社製）を用いた以外は、実施例７と同様に反応を行った。結果を表１－１に示す。 (Example 11)
The reaction was carried out in the same manner as in Example 7 except that 5% palladium-supported carbon (5% Pd / C) (manufactured by Wako Pure Chemical Industries, Ltd.) was used as the catalyst. The results are shown in Table 1-1.
　（実施例１２）
　触媒に金担持ハイドロタルサイト（Ａｕ／ＨＴ）（富士フイルム和光純薬株式会社製）を用いた以外は、実施例７と同様に反応を行った。結果を表１－１に示す。 (Example 12)
The reaction was carried out in the same manner as in Example 7 except that gold-supported hydrotalcite (Au / HT) (manufactured by Wako Pure Chemical Industries, Ltd.) was used as a catalyst. The results are shown in Table 1-1.
　（実施例１３）
　内容量１００ｍＬのステンレス製反応容器（耐圧硝子工業株式会社製）に、参考例２で調製したα－ヒドロムコン酸ジメチル１４４ｍｇ、アセトニトリル５０ｍＬ（ＭｅＣＮ、国産化学株式会社製）、脱水素化触媒として５％パラジウム担持炭素（５％Ｐｄ／Ｃ）１００ｍｇ（富士フイルム和光純薬株式会社製）を添加した。撹拌速度５００ｒｐｍで撹拌しながら、反応容器を窒素分圧０．５ＭＰａ（ゲージ圧）となるように窒素を導入し、次いで、反応容器内の温度を２００℃に昇温した。２時間２００℃で保持した後、室温まで放冷した。反応容器内のガスを放出して常圧に戻した後、反応溶液を回収した。遠心分離により触媒を除去して得た上清をＧＣにより分析し、ｔｒａｎｓ，ｔｒａｎｓ－ムコン酸ジメチルの収量を算出した。結果を表１－１に示す。 (Example 13)
144 mg of dimethyl α-hydromuconate prepared in Reference Example 2, 50 mL of acetonitrile (MeCN, manufactured by Kokusan Kagaku Co., Ltd.), 5% as a dehydrogenation catalyst in a stainless steel reaction vessel (manufactured by Pressure Resistant Glass Industry Co., Ltd.) with an internal volume of 100 mL. 100 mg of palladium-supported carbon (5% Pd / C) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added. While stirring at a stirring speed of 500 rpm, nitrogen was introduced into the reaction vessel so that the partial pressure of nitrogen was 0.5 MPa (gauge pressure), and then the temperature inside the reaction vessel was raised to 200 ° C. After holding at 200 ° C. for 2 hours, the mixture was allowed to cool to room temperature. After releasing the gas in the reaction vessel and returning it to normal pressure, the reaction solution was recovered. The supernatant obtained by removing the catalyst by centrifugation was analyzed by GC, and the yields of trans and trans-dimethyl muconate were calculated. The results are shown in Table 1-1.
　（実施例１４）
　溶媒にｔｅｒｔ－ブタノール５０ｍＬ（ｔ－ＢｕＯＨ、富士フイルム和光純薬株式会社製）を用いた以外は実施例１３と同様に反応を行った。結果を表１－１に示す。 (Example 14)
The reaction was carried out in the same manner as in Example 13 except that 50 mL of tert-butanol (t-BuOH, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was used as the solvent. The results are shown in Table 1-1.
　（実施例１５）
　窒素の代わりに空気を導入した以外は実施例１３と同様に反応を行った。結果を表１－１に示す。 (Example 15)
The reaction was carried out in the same manner as in Example 13 except that air was introduced instead of nitrogen. The results are shown in Table 1-1.
　（実施例１６）
　溶媒にＮ，Ｎ－ジメチルアセトアミド（ＤＭＡ、富士フイルム和光純薬株式会社製）を用いた以外は実施例１５と同様に反応を行った。結果を表１－１に示す。 (Example 16)
The reaction was carried out in the same manner as in Example 15 except that N, N-dimethylacetamide (DMA, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was used as the solvent. The results are shown in Table 1-1.
　（実施例１７）
　反応温度を２５０℃にした以外は実施例１３と同様に反応を行った。結果を表１－１に示す。 (Example 17)
The reaction was carried out in the same manner as in Example 13 except that the reaction temperature was set to 250 ° C. The results are shown in Table 1-1.
　（実施例１８）
　内容量１００ｍＬのステンレス製反応容器（耐圧硝子工業株式会社製）に、参考例２で調製したα－ヒドロムコン酸ジメチル１４４ｍｇ、Ｎ，Ｎ－ジメチルアセトアミド３０ｍＬ（ＤＭＡ、富士フイルム和光純薬株式会社製）、脱水素化触媒として５％パラジウム担持炭素（５％Ｐｄ／Ｃ）１００ｍｇ（富士フイルム和光純薬株式会社製）を添加した。撹拌速度５００ｒｐｍで撹拌しながら、反応容器を窒素分圧０．５ＭＰａ（ゲージ圧）となるように窒素を導入し、次いで、反応容器内の温度を１５０℃に昇温した。６時間１５０℃で保持した後、室温まで放冷した。反応容器内のガスを放出して常圧に戻した後、反応溶液を回収した。遠心分離により触媒を除去して得た上清をＧＣにより分析し、ｔｒａｎｓ，ｔｒａｎｓ－ムコン酸ジメチルの収量を算出した。結果を表１－１に示す。 (Example 18)
In a stainless steel reaction vessel (manufactured by Pressure-Resistant Glass Industry Co., Ltd.) with an internal volume of 100 mL, 144 mg of dimethyl α-hydromuconate prepared in Reference Example 2 and 30 mL of N, N-dimethylacetamide (DMA, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) , 100 mg of 5% palladium-supported carbon (5% Pd / C) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added as a dehydrogenation catalyst. While stirring at a stirring speed of 500 rpm, nitrogen was introduced into the reaction vessel so that the partial pressure of nitrogen was 0.5 MPa (gauge pressure), and then the temperature inside the reaction vessel was raised to 150 ° C. After holding at 150 ° C. for 6 hours, the mixture was allowed to cool to room temperature. After releasing the gas in the reaction vessel and returning it to normal pressure, the reaction solution was recovered. The supernatant obtained by removing the catalyst by centrifugation was analyzed by GC, and the yields of trans and trans-dimethyl muconate were calculated. The results are shown in Table 1-1.
　（実施例１９）
　反応温度を１１０℃、反応時間を５時間にした以外は実施例１８と同様に反応を行った。結果を表１－２に示す。 (Example 19)
The reaction was carried out in the same manner as in Example 18 except that the reaction temperature was 110 ° C. and the reaction time was 5 hours. The results are shown in Table 1-2.
　（実施例２０）
　窒素分圧を大気圧、反応温度を１００℃、反応時間を１３時間にした以外は実施例１８と同様に反応を行った。結果を表１－２に示す。 (Example 20)
The reaction was carried out in the same manner as in Example 18 except that the nitrogen partial pressure was atmospheric pressure, the reaction temperature was 100 ° C., and the reaction time was 13 hours. The results are shown in Table 1-2.
　（実施例２１）
　内容量１００ｍＬのステンレス製反応容器（耐圧硝子工業株式会社製）に、参考例２で調製したα－ヒドロムコン酸ジメチル１４４ｍｇ、アセトニトリル２５ｍＬ（ＭｅＣＮ、国産化学株式会社製）、脱水素化触媒として５％パラジウム担持炭素（５％Ｐｄ／Ｃ）１００ｍｇ（富士フイルム和光純薬株式会社製）を添加した。撹拌速度５００ｒｐｍで撹拌しながら、反応容器を窒素分圧０．５ＭＰａ（ゲージ圧）となるように窒素を導入し、次いで、反応容器内の温度を２００℃に昇温した。２０時間２００℃で保持した後、室温まで放冷した。反応容器内のガスを放出して常圧に戻した後、反応溶液を回収した。遠心分離により触媒を除去して得た上清をＧＣにより分析し、ｔｒａｎｓ，ｔｒａｎｓ－ムコン酸ジメチルの収量を算出した。結果を表１－２に示す。 (Example 21)
144 mg of dimethyl α-hydromuconate prepared in Reference Example 2, 25 mL of acetonitrile (MeCN, manufactured by Kokusan Kagaku Co., Ltd.), 5% as a dehydrogenation catalyst in a stainless steel reaction vessel (manufactured by Pressure Resistant Glass Industry Co., Ltd.) with an internal volume of 100 mL. 100 mg of palladium-supported carbon (5% Pd / C) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added. While stirring at a stirring speed of 500 rpm, nitrogen was introduced into the reaction vessel so that the partial pressure of nitrogen was 0.5 MPa (gauge pressure), and then the temperature inside the reaction vessel was raised to 200 ° C. After holding at 200 ° C. for 20 hours, the mixture was allowed to cool to room temperature. After releasing the gas in the reaction vessel and returning it to normal pressure, the reaction solution was recovered. The supernatant obtained by removing the catalyst by centrifugation was analyzed by GC, and the yields of trans and trans-dimethyl muconate were calculated. The results are shown in Table 1-2.
　（実施例２２）
　触媒に５％パラジウム担持アルミナ（５％Ｐｄ／Ａｌ２Ｏ３）（ＡｌｆａＡｅｓａｒ社製）を用いた以外は実施例２１と同様に反応を行った。結果を表１－２に示す。 (Example 22)
The reaction was carried out in the same manner as in Example 21 except that 5% palladium-supported alumina (5% Pd / Al 2 O 3) (manufactured by Alfa Aesar) was used as the catalyst. The results are shown in Table 1-2.
　（実施例２３）
　反応温度を１５０℃にした以外は実施例２１と同様に反応を行った。結果を表１－２に示す。 (Example 23)
The reaction was carried out in the same manner as in Example 21 except that the reaction temperature was set to 150 ° C. The results are shown in Table 1-2.
　（実施例２４）
　内容量１０ｍＬのガラス製反応容器に、参考例２で調製したα－ヒドロムコン酸ジメチル１４４ｍｇ、アセトニトリル３ｍＬ（ＭｅＣＮ、国産化学株式会社製）、脱水素化触媒として２０％パラジウム担持炭素（２０％Ｐｄ／Ｃ）１００ｍｇ（エヌ・イー　ケムキャット株式会社製）を添加した。撹拌速度５００ｒｐｍで撹拌しながら、反応容器内に１ｍＬ／ｍｉｎの流速で窒素を流通させた状態で、反応容器内の温度を１５０℃に昇温し、反応容器内の溶媒を揮発させた。１５０℃に昇温してから３時間保持した後、室温になるまで放冷した。アセトニトリルを加えて２０ｍＬにメスアップした溶液から遠心分離により触媒を除去して得た上清をＧＣにより分析し、ｔｒａｎｓ，ｔｒａｎｓ－ムコン酸ジメチルの収量を算出した。結果を表１－２に示す。 (Example 24)
In a glass reaction vessel with an internal volume of 10 mL, 144 mg of dimethyl α-hydromuconate prepared in Reference Example 2, 3 mL of acetonitrile (MeCN, manufactured by Kokusan Kagaku Co., Ltd.), and 20% palladium-supported carbon (20% Pd /) as a dehydrogenation catalyst. C) 100 mg (manufactured by NT Co., Ltd.) was added. While stirring at a stirring speed of 500 rpm, the temperature inside the reaction vessel was raised to 150 ° C. while nitrogen was flowing through the reaction vessel at a flow rate of 1 mL / min to volatilize the solvent in the reaction vessel. After raising the temperature to 150 ° C. and holding it for 3 hours, it was allowed to cool until it reached room temperature. The supernatant obtained by removing the catalyst by centrifugation from the solution prepared by adding acetonitrile to 20 mL was analyzed by GC, and the yields of trans and trans-dimethyl muconate were calculated. The results are shown in Table 1-2.
　（実施例２５）
　アセトニトリル（ＭｅＣＮ、国産化学株式会社製）を３０ｍＬ用いて、反応容器内の温度を２００℃で３時間保持した以外は実施例１３と同様に反応行った。結果を表１－２に示す。 (Example 25)
The reaction was carried out in the same manner as in Example 13 except that 30 mL of acetonitrile (MeCN, manufactured by Kokusan Kagaku Co., Ltd.) was used and the temperature in the reaction vessel was maintained at 200 ° C. for 3 hours. The results are shown in Table 1-2.
　（実施例２６）
　反応温度を１５０℃にした以外は実施例２５と同様に反応行った。結果を表１－２に示す。 (Example 26)
The reaction was carried out in the same manner as in Example 25 except that the reaction temperature was set to 150 ° C. The results are shown in Table 1-2.
　（比較例１）
　金－パラジウム担持ハイドロタルサイト（ＡｕＰｄ／ＨＴ）を加えなかったことを除いては実施例７と同様に反応を行った。結果を表１－２に示す。 (Comparative Example 1)
The reaction was carried out in the same manner as in Example 7 except that gold-palladium-supported hydrotalcite (AuPd / HT) was not added. The results are shown in Table 1-2.
　（比較例２）
　５％パラジウム担持炭素（５％Ｐｄ／Ｃ）を加えなかったことを除いては実施例２３と同様に反応を行った。結果を表１－２に示す。 (Comparative Example 2)
The reaction was carried out in the same manner as in Example 23 except that 5% palladium-supported carbon (5% Pd / C) was not added. The results are shown in Table 1-2.
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008
　実施例、比較例より、α－ヒドロムコン酸又はそのアルキルエステルを、脱水素化触媒の存在下、脱水素化することにより、ｔｒａｎｓ，ｔｒａｎｓ－ムコン酸又はそのアルキルエステルを製造できることが示された。 From Examples and Comparative Examples, it was shown that trans, trans-muconic acid or an alkyl ester thereof can be produced by dehydrogenating α-hydromuconic acid or an alkyl ester thereof in the presence of a dehydrogenation catalyst.

Claims (4)

  1. 　α－ヒドロムコン酸又はそのアルキルエステルを、脱水素化触媒の存在下、脱水素化する工程を含む、ｔｒａｎｓ，ｔｒａｎｓ－ムコン酸又はそのアルキルエステルの製造方法。 A method for producing trans, trans-muconic acid or an alkyl ester thereof, which comprises a step of dehydrogenating α-hydromuconic acid or an alkyl ester thereof in the presence of a dehydrogenation catalyst.
  2. 　前記α－ヒドロムコン酸又はそのアルキルエステルおよび前記ｔｒａｎｓ，ｔｒａｎｓ－ムコン酸又はそのアルキルエステルが、それぞれ以下の一般式（Ｉ）および（ＩＩ）で示される化合物である、請求項１に記載の方法。
    Figure JPOXMLDOC01-appb-C000001
     ［式中、Ｒ１及びＲ２はそれぞれ独立に水素原子又は炭素数１～５のアルキルを表す。］     The method according to claim 1, wherein the α-hydromuconic acid or an alkyl ester thereof and the trans, trans-muconic acid or an alkyl ester thereof are compounds represented by the following general formulas (I) and (II), respectively.
    Figure JPOXMLDOC01-appb-C000001
     [In the formula, R 1 and R 2 independently represent a hydrogen atom or an alkyl having 1 to 5 carbon atoms, respectively. ]
  3. 　前記脱水素化する工程が水素ガスを導入しない工程である、請求項１又は２に記載の方法。 The method according to claim 1 or 2, wherein the dehydrogenation step is a step in which hydrogen gas is not introduced.
  4. 　前記脱水素化触媒が金及び／又はパラジウムを含む触媒である、請求項１～３のいずれかに記載の方法。 The method according to any one of claims 1 to 3, wherein the dehydrogenation catalyst is a catalyst containing gold and / or palladium.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006500430A (en) * 2002-09-27 2006-01-05 ビーエーエスエフ アクチェンゲゼルシャフト Process for the production of at least one partial oxidation and / or ammoxidation product of propylene
JP2006528605A (en) * 2003-07-24 2006-12-21 ビーエーエスエフ　アクチェンゲゼルシャフト Method for producing unsaturated carbonyl compound
WO2012082725A1 (en) * 2010-12-15 2012-06-21 Amyris, Inc. Continuous dehydrogenation of 1,4-carboxylate substituted cyclohexenes
WO2016199858A1 (en) * 2015-06-10 2016-12-15 東レ株式会社 METHOD FOR PRODUCING α-HYDROMUCONIC ACID
CN109896918A (en) * 2017-12-08 2019-06-18 北京大学深圳研究生院 Beta-unsaturated carbonyl compounds and its preparation method and application
CN110483265A (en) * 2019-08-02 2019-11-22 西北大学 A kind of synthetic method of two olefine aldehydr or diene ketone compounds

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006500430A (en) * 2002-09-27 2006-01-05 ビーエーエスエフ アクチェンゲゼルシャフト Process for the production of at least one partial oxidation and / or ammoxidation product of propylene
JP2006528605A (en) * 2003-07-24 2006-12-21 ビーエーエスエフ　アクチェンゲゼルシャフト Method for producing unsaturated carbonyl compound
WO2012082725A1 (en) * 2010-12-15 2012-06-21 Amyris, Inc. Continuous dehydrogenation of 1,4-carboxylate substituted cyclohexenes
WO2016199858A1 (en) * 2015-06-10 2016-12-15 東レ株式会社 METHOD FOR PRODUCING α-HYDROMUCONIC ACID
CN109896918A (en) * 2017-12-08 2019-06-18 北京大学深圳研究生院 Beta-unsaturated carbonyl compounds and its preparation method and application
CN110483265A (en) * 2019-08-02 2019-11-22 西北大学 A kind of synthetic method of two olefine aldehydr or diene ketone compounds

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