Classifications

• • 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.

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