WO2019017490A1 - Production method for pentenoic acid ester derivative - Google Patents

Abstract

The invention relates to a process for producing a pentenoic acid ester derivative using a biomass raw material, comprising step A, which comprises reacting the biomass raw material with a first alcohol in the presence of an acid catalyst to obtain a levulinic acid ester and a formic acid ester, step B which comprises reacting the levulinic acid ester with a source of hydrogen to obtain γ-valerolactone and step C which comprises reacting γ-valerolactone with a second alcohol in the presence of an acid catalyst or a basic catalyst to obtain a pentenoic acid ester.

Description

Process for producing pentenoic acid ester derivative

The present invention relates to a method for producing a pentenoic acid ester derivative.

Adipic acid and its esters are useful precursors used as raw materials for various organic chemicals such as nylon 6,6, urethanes, plasticizers and the like.

Currently, chemical synthesis methods are known as methods for producing adipic acid and esters thereof. As a chemical synthesis method, for example, a method of oxidizing cyclohexanol alone or a mixture of cyclohexanol and cyclohexanone (K / A oil) with nitric acid is known. On the other hand, recently, from the viewpoint of global warming prevention and environmental protection, it has been attracting attention to use recyclable biological resources as a carbon source as a substitute for conventional fossil materials, and so far, fermentation methods of microorganisms have been used Methods for producing adipic acid have also been developed.

For example, Patent Document 1 discloses a method for producing adipic acid in which a microorganism belonging to the genus Alcaligenes having the ability to produce adipic acid from cyclohexanol, cyclohexanone or a mixture thereof is caused to act on cyclohexanol, cyclohexanone or a mixture thereof. It is disclosed.

Further, Non-Patent Document 1 discloses a method in which a microorganism belonging to the genus Acinetobacter, assimilates cyclohexanol to produce adipic acid. However, this method utilizes a precursor derived from fossil raw materials, and Non-Patent Document 1 does not disclose the utilization of a biological source.

As for those using a biological source, for example, in Patent Document 2, a biorelevant carbon source is converted to cis, cis-muconic acid using a recombinant, and cis, cis-muconic acid is hydrogenated to adipine. A method of producing an acid is disclosed. Patent Document 3 discloses a method for producing adipic acid from α-ketoglutaric acid using a recombinant.

In addition, Patent Document 4 discloses a large number of engineered microorganisms host cells capable of synthesizing a carbon-based compound from carbon dioxide and water. The Rhodobacter genus is described as one example of a large number of enumerated microorganisms, and adipic acid is described as one of a large number of synthesizable carbon-based compounds. However, all of these use a microorganism in which a gene has been recombined, and Patent Document 4 does not show an example of synthesizing adipic acid.

Patent Document 5 discloses a method for producing adipic acid from glucose via glucan acid. Further, Non-Patent Document 2 discloses a method for producing adipic acid via catechol muconic acid.

In Patent Document 6, biomass feedstock is steamed at high temperature to synthesize 5-hydroxymethylfurfural, which is hydrogenated in the presence of Raney Nickel catalyst to synthesize 2,5-tetrahydroxy flange methanol, and the like. Hydrogenating the obtained 2,5-tetrahydroxyfuranmethanol in the presence of a copper catalyst under predetermined temperature and pressure conditions to synthesize 1,6-hexanediol and further oxidizing in the presence of microorganisms A process for producing adipic acid is disclosed.

JP-A-64-23894 International Publication No. 1995/007996 WO 2010/104391 WO 2009/111513 U.S. Patent Application Publication No. 2011/0218318 U.S. Pat. No. 4,400,468

Eur. J. Biochem. , 1975, 60 volumes, pp. 1-7 Biotechnol. Prog. , 2002, 18 volumes, pp. 201-211

Currently, crude products are mainly used as chemical products. Chemical products are mainly composed of carbon atoms, and the carbon finally becomes carbon dioxide and is accumulated in the atmosphere. Since carbon dioxide accumulated in the atmosphere causes global warming, it is strongly desired to reduce carbon dioxide emissions.

One possible solution is to use biomass feedstock (eg, cellulose, glucose, vegetable oil, etc.), which is a plant-derived resource, as a starting material for chemical products. The reason is that the plant that is the source of the biomass feedstock absorbs carbon dioxide by photosynthesis in its growth process, and the absorbed amount of carbon dioxide offsets the carbon dioxide emissions from the combustion of chemical products. is there.

The inventors of the present invention have newly found a method for efficiently synthesizing a pentenoic acid ester that can be used as a precursor of adipic acid and esters thereof from biomass raw materials.

Then, an object of this invention is to provide the method of manufacturing a pentenoic-acid-ester derivative efficiently from biomass raw material.

The present inventors have found that pentenoic acid ester derivatives such as adipic acid compounds, 1,6-hexanediol, 1,3-butadiene, ε-caprolactam and the like can be produced using biomass raw materials, and completed the present invention.

That is, in one aspect, the present invention is a method for producing a pentenoic acid ester derivative using a biomass material, which comprises reacting a biomass material with a first alcohol in the presence of an acid catalyst to obtain levulinate ester and formate ester. Obtaining step A, reacting levulinate with hydrogen source to obtain .gamma.-valerolactone B, and reacting .gamma.-valerolactone with a second alcohol in the presence of an acid catalyst or a base catalyst to obtain pentenoate Providing a step C of obtaining

In the said manufacturing method, by passing process A, B, and C, a pentenoic acid ester derivative can be efficiently manufactured from a biomass raw material. Moreover, in the above manufacturing method, it is possible to contribute to sustainable development since it is not necessary to use petroleum-derived raw materials.

Preferably, in step A, the first alcohol comprises methanol. Preferably, in step B, the hydrogen source comprises hydrogen gas. Preferably, in step C, the second alcohol comprises methanol. By this, a pentenoic acid ester derivative can be manufactured more efficiently.

The method for producing a pentenoic acid ester derivative may further include the step D of reacting a pentenoic acid ester with a formic acid ester in the presence of a complex metal to obtain an adipic acid compound.

The formic acid ester in step D preferably contains the formic acid ester obtained in step A. This makes it possible to more effectively utilize the biomass material.

The process for producing a pentenoic acid ester derivative may further include, after step D, step E of hydrolyzing the adipic acid compound.

In one aspect of the present invention, the process for producing a pentenoic acid ester derivative further comprising step D may further comprise step F of reacting an adipic acid compound with a hydrogen source to obtain 1,6-hexanediol.

In one aspect of the present invention, the method for producing a pentenoic acid ester derivative further comprises the step G of reacting pentenoic acid ester, water and an acid anhydride in the presence of a complex metal to obtain 1,3-butadiene. Good.

Further, in one aspect of the present invention, a method for producing a pentenoic acid ester derivative comprises reacting pentenoic acid ester with water in the presence of an acid catalyst to obtain butene (a mixture of 1-butene and 2-butene), butene The method may further include the step of dehydrogenating (a mixture of 1-butene and 2-butene) in the presence of a metal oxide catalyst to obtain 1,3-butadiene.

In one aspect of the present invention, a process for producing a pentenoic acid ester derivative comprises reacting a pentenoic acid ester with carbon monoxide and hydrogen in the presence of a complex metal to obtain 5-formylpentanoic acid ester. The method may further comprise the step I of reacting formylpentanoic acid ester, ammonia and a hydrogen source to obtain ε-caprolactam.

The biomass material is wood, sawdust, wood flour, bark, paper, pulp, paper waste, bagasse, rice husk, coconut husk, rice husk, rice bran, rice bran, soybean meal, rapeseed meal, coffee meal, tea meal, okara, It may contain at least one selected from the group consisting of corn cob, corn stover, coconut hair, switchgrass, alfalfa, bamboo, grass, hay, seaweed and seaweed.

In the method for producing a pentenoic acid ester derivative, the first alcohol or the second alcohol may be the alcohol obtained in step B.

The present invention provides, in one aspect, a pentenoate ester having a biomass degree of 40% or more as determined by accelerator mass spectrometry.

ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the method of manufacturing a pentenoic acid ester derivative efficiently from a biomass raw material.

Hereinafter, an embodiment of the present invention will be described. However, the following embodiments are exemplifications for describing the present invention, and the present invention is not intended to be limited to the following contents.

In the method for producing a pentenoic acid ester derivative according to the present embodiment, the levulinic acid ester obtained in step A and step A is obtained by reacting a biomass raw material and a first alcohol in the presence of an acid catalyst to obtain levulinic acid ester and formate ester. Is reacted with a hydrogen source to obtain γ-valerolactone. The γ-valerolactone obtained in step B and step B is reacted with a second alcohol in the presence of an acid catalyst or a base catalyst to obtain a pentenoate ester. Step C is included. The pentenoic acid ester derivatives are compounds derivable from pentenoic acid esters. Pentenic acid ester derivatives include, for example, adipic acid compounds, 1,6-hexanediol, 1,3-butadiene, 5-formylpentanoic acid ester and ε-caprolactam.

　一般式（１）及び一般式（２）中、Ｒは炭素原子数１～６の直鎖状のアルキル基、又は炭素原子数３～６の分岐状のアルキル基を示す。 (Step A)
In step A, as shown in the following reaction formula (I), a biomass feedstock and a first alcohol (ROH) are reacted in the presence of an acid catalyst to obtain levulinic acid ester and formate ester. In the following reaction formula (I), the general formula (1) represents levulinic acid ester, and the general formula (2) represents a formic acid ester.

In the general formula (1) and the general formula (2), R represents a linear alkyl group having 1 to 6 carbon atoms or a branched alkyl group having 3 to 6 carbon atoms.

The biomass material used in step A is a renewable, plant-derived organic resource from which fossil resources (oil-derived materials) have been removed. The biomass feedstock contains cellulose and hemicellulose. As biomass raw materials, various wood such as cedar, rice pine, eucalyptus, sawdust, wood flour, bark, paper, pulp, paper waste, bagasse, rice husk, coconut husk, coconut husk, rice bran, rice bran, soybean meal, rapeseed meal, coffee There may be mentioned rice bran, rice bran, okara, corn cob, corn stover, coconut hair, switchgrass, alfalfa, bamboo, grass, hay, seaweed, seaweed and the like. In this embodiment, the biomass material is wood, sawdust, wood flour, bark, paper, pulp, paper waste, bagasse, rice husk, coconut husk, coconut husk, rice bran, rice bran, soybean meal, rapeseed meal, coffee meal, tea meal It is preferable that at least one selected from the group consisting of okara, corn cob, corn stover, coconut hair, switchgrass, alfalfa, bamboo, grass, hay, seaweed and seaweed.

The biomass raw material may be used individually by 1 type among the above-mentioned various raw materials, and may be used combining 2 or more types. When the biomass material is a mixture of two or more, the mixture may be used as it is without isolation. In addition, the biomass material may contain water. The biomass raw material may be supplied as a raw material of step A in a water-containing state (hydrous state), or may be supplied in a dry state (through a drying step).

The first alcohol (ROH) used in step A has a linear alkyl group having 1 to 6 carbon atoms or a branched alkyl group having 3 to 6 carbon atoms. Examples of the first alcohol include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 1-hexanol, 2- Hexanol and 3-hexanol can be mentioned. The first alcohol is preferably at least one selected from the group consisting of methanol, ethanol, 1-propanol and 1-butanol, more preferably methanol. The first alcohol may be used alone or in combination of two or more. When the first alcohol is a combination of two or more alcohols, levulinic acid esters and formate esters having different kinds of alkyl groups may be formed.

The amount of the first alcohol used is not particularly limited, but is preferably 200 to 3000 parts by mass, more preferably 400 to 1500 parts by mass, with respect to 100 parts by mass of the total amount of biomass raw materials. The first alcohol may be used as a reaction solvent in step A.

Examples of the acid catalyst used in step A include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, and organic acids such as carboxylic acid and sulfonic acid (organic sulfonic acid). The acid catalyst is preferably sulfuric acid or sulfonic acid.

Examples of the sulfonic acid include alkylsulfonic acid having 1 to 6 carbon atoms such as methanesulfonic acid, ethanesulfonic acid, hexanesulfonic acid, methanedisulfonic acid, ethanedisulfonic acid, propanedisulfonic acid, and butanedisulfonic acid; benzenesulfone Acids, p-toluenesulfonic acid, naphthalenesulfonic acid, naphthalenedisulfonic acid, anthracenesulfonic acid, anthracenedisulfonic acid, pyrenesulfonic acid, and arylsulfonic acids having 6 to 24 carbon atoms such as pyrenesulfonic acid; and camphorsulfonic acid Be The sulfonic acid preferably contains at least one selected from the group consisting of benzenesulfonic acid, p-toluenesulfonic acid and naphthalenesulfonic acid, and more preferably p-toluenesulfonic acid.

The amount of the acid catalyst used is preferably 0.5 to 30 parts by mass, more preferably 1 to 20 parts by mass with respect to 100 parts by mass of sugar (cellulose and hemicellulose) converted biomass feedstock.

In step A, in addition to the above-mentioned acid catalyst, additives described later may be used. By combining the additive and the above-mentioned acid catalyst, levulinic acid ester can be obtained in higher yield.

The additive preferably contains an element (group 13 element or group 14 element) belonging to group 13 or 14 in the periodic table, and boron, aluminum, gallium, indium, germanium, tin, and lead It is more preferable to include at least one element selected from the group consisting of, more preferably to contain aluminum or indium, and even more preferably to contain aluminum. Here, when the additive contains a Group 13 metal element or a Group 14 metal element, the additive is also referred to as a metal compound.

The additive (metal compound) may be at least one selected from the group consisting of hydroxide salts, sulfates, nitrates, carboxylates, alkoxides, acetylacetone salts and oxides. Among these, more preferably, they are hydroxide salts, sulfates, alkoxides or acetylacetone salts. The additive (metal compound) may be used in the form of a salt soluble in the solvent (for example, the first alcohol) used in step A, and the solvent (for example, the first alcohol) used in step A ) May be used in the form of a salt insoluble in

The amount of the additive (metal compound) used is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of sugar (cellulose and hemicellulose) equivalent constituting the biomass material, and more preferably 0. 5 to 5 parts by mass.

The reaction temperature for carrying out the reaction of step A is preferably 160 to 230 ° C., more preferably 170 to 200 ° C. When the reaction temperature is 160 ° C. or more, a sufficient reaction rate can be secured. In addition, when the reaction temperature is 230 ° C. or less, suppressing the reduction in the yield of levulinate ester due to the formation of an ether compound by the intermolecular dehydration reaction of alcohol and by-production of humic substances from the sugars constituting the biomass material Can. By setting the reaction temperature to 170 to 200 ° C., the above effects can be achieved at a higher level.

The reaction pressure for carrying out the reaction of step A is not particularly limited, but it is preferably 1 to 8 MPa, more preferably 3 to 5 MPa. When the reaction pressure is 1 MPa or more, the reduction of the reaction efficiency due to the vaporization of the solvent (for example, the first alcohol) tends to be suppressed. When the reaction pressure is 8 MPa or less, the cost of the reactor tends to be suppressed.

The yield of levulinic acid ester in step A is preferably 40% or more, more preferably 60% or more. The yield of levulinic acid ester in the present disclosure is a yield on a molar basis based on the content of cellulose contained in the biomass feedstock. The levulinic acid ester obtained by process A can be used as a raw material of process B mentioned later.

The yield of formate in step A is preferably 50% or more, more preferably 65% or more. The yield of levulinic acid ester in the present disclosure is a yield on a molar basis based on the content of cellulose contained in the biomass feedstock. The formate ester obtained by step A is suitably used as a raw material of step D.

In the present embodiment, in step A, a reaction liquid containing levulinic acid ester and formate ester can be obtained. In the present embodiment, after step A, a step of separating levulinic acid ester and formic acid ester (step A ′) may be included. Levulinic acid ester and formate ester can be separated, for example, by distillation. The conditions of the distillation treatment are appropriately selected according to the type of biomass material and first alcohol used. The distillation process in formic acid ester separation is carried out, for example, at a temperature condition of 10 to 100 ° C. and a pressure condition of 40 kPa to normal pressure. In addition, the distillation process in levulinic acid ester separation is performed, for example, at a temperature condition of 50 to 200 ° C. and a pressure condition of 1.0 kPa to normal pressure.

After completion of the above step A or step A ′, a general operation such as filtration, concentration, extraction, distillation, sublimation, recrystallization, column chromatography, etc. on the solution containing levulinic acid ester and / or formate ester Levulinic acid ester or formate ester may be purified by performing the purification step).

　反応式（ＩＩ）中、Ｒは炭素原子数１～６の直鎖状のアルキル基、又は炭素原子数３～６の分岐状のアルキル基を示す。 (Step B)
In step B, as shown in the following reaction formula (II), the levulinic acid ester (compound represented by general formula (1)) obtained in step A is reacted with a hydrogen source to give γ-valerolactone obtain. In the following reaction formula (II), the general formula (3) represents γ-valerolactone.

In the reaction formula (II), R represents a linear alkyl group having 1 to 6 carbon atoms or a branched alkyl group having 3 to 6 carbon atoms.

In step B, the levulinic acid ester obtained in step A is used. The levulinic acid ester used here is preferably suitably purified by distillation or the like.

The hydrogen source used in step B is not particularly limited. Specifically, for example, hydrogen gas, alcohol, formic acid, hydrazine, sodium borohydride, lithium aluminum hydride and the like can be mentioned. The hydrogen source is preferably hydrogen gas from the viewpoint of easy separation and purification after completion of the reaction.

In step B, levulinic acid ester and a hydrogen source are reacted in the presence of a hydrogenation catalyst. The hydrogenation (hydrogenation) catalyst used in step B is a catalyst containing a metal element, and any catalyst can be selected as long as it can hydrogenate (hydrogenate) carbonyl compounds such as ketones and aldehydes. The hydrogenation catalyst preferably contains one kind of metal element such as nickel (Ni), copper (Cu), ruthenium (Ru), rhodium (Rh), palladium (Pd), iridium (Ir), platinum (Pt), etc. Or it is a solid catalyst containing 2 or more types, More preferably, it is a solid catalyst containing copper (Cu).

The total content of the above-mentioned metal elements in the hydrogenation (hydrogenation) catalyst is preferably 1% by mass to 80% by mass, and more preferably 5% by mass to 60%, based on the total mass of the hydrogenation catalyst. It is less than mass%. The metal element contained in the hydrogenation catalyst may be present as a zero-valent metal or metal oxide. When the ratio of metal oxides is high, reduction treatment may be performed in advance with hydrogen gas or the like before the reaction, or may be used for the reaction as it is.

The hydrogenation catalyst may contain a carrier. As the carrier, porous ones are suitably used. For example, porous silica, porous alumina, porous silica alumina (aluminosilicate), porous ceria, porous magnesia, porous calcia, porous titania, porous Silica (titanosilicate), porous zirconia, activated carbon, zeolite, mesoporous material (mesoporous-alumina, mesoporous-silica, mesoporous-carbon) and the like. The support preferably includes porous silica, porous alumina, porous activated carbon, and porous zeolite. These carriers may be used alone or in combination of two or more.

The said hydrogenation catalyst may contain the other metallic element other than the metallic element mentioned above. Other metallic elements may be present as zero-valent metals or metal oxides. Examples of other metal elements include chromium (Cr), manganese (Mn), rhenium (Re), zinc (Zn), magnesium (Mg), sodium (Na), calcium (Ca) and the like.

In the reaction of step B, either a batch system (batch system) or a continuous system can be selected. In addition, depending on the nature of the hydrogenation catalyst, it can be carried out in both homogeneous and heterogeneous (suspension reaction) reaction systems.

When the reaction of step B is carried out batchwise, for example, a hydrogenation catalyst and levulinic acid ester are mixed and reacted while stirring under a hydrogen atmosphere.

When the reaction of step B is carried out continuously, for example, hydrogen and levulinic acid ester are allowed to flow in a reaction tube filled with a hydrogenation catalyst. In addition, if necessary, an inert solid charge that supports the charge of the catalyst in the reaction tube may be disposed in the reaction tube.

The reaction temperature for carrying out the reaction of step B is preferably 50 to 220 ° C., more preferably 80 to 200 ° C. Further, the reaction pressure at the time of carrying out the reaction of step B is, as a hydrogen partial pressure, normal pressure to 10 MPa, more preferably normal pressure to 5 MPa.

The reaction temperature and reaction pressure may be changed intermittently or continuously within the relevant range. By setting the reaction temperature and the reaction pressure in the above ranges, it is possible to obtain γ-valerolactone in a high yield and highly selectively at a high reaction rate while suppressing the formation of by-products.

In the reaction of step B, a solvent may be used to facilitate the supply of levulinic acid ester as a raw material and to improve the stirring property in a batch system, or to improve the flowability in a continuous system, etc. . The solvent used in step B is not particularly limited as long as it does not significantly inhibit the reaction, and, for example, water; methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, tert-butyl alcohol, and Alcohols such as ethylene glycol; Hydrocarbons such as heptane, hexane, cyclohexane and toluene; Amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone; Diethyl ether , Ethers such as diisopropyl ether, 1,2-dimethoxyethane, 1,2-diethoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, tetrahydrofuran, and dioxane; methylene chloride, dichloro ether Emissions, and halogenated hydrocarbons such as chloro cyclohexane. Among these, preferably, at least one selected from the group consisting of water, alcohols, hydrocarbons and ethers is used, and more preferably alcohols are used. In addition, one of these solvents may be used alone, or two or more thereof may be used in combination.

The amount of the solvent used in step B is preferably 0 to 100 parts by mass, more preferably 0 to 50 parts by mass, with respect to 1 part by mass of levulinic acid ester. By setting the amount of solvent used in this range, stirring or circulation can be rapidly performed, and the reaction can be smoothly progressed.

The conversion of levulinic acid ester in step B is preferably 80% or more, more preferably 90% or more, and still more preferably 95%. The conversion of levulinate in the present disclosure is on a molar basis.

The yield of γ-valerolactone in step B is preferably 80% or more, more preferably 90% or more, and still more preferably 95%. The yield of γ-valerolactone in the present disclosure is a yield on a molar basis based on levulinic acid ester.

In the present embodiment, in step B, a reaction liquid containing γ-valerolactone can be obtained. After completion of the step B, the obtained reaction liquid is subjected to general operations (purification step) such as filtration, concentration, extraction, distillation, sublimation, recrystallization, column chromatography, etc. Valerolactone may be isolated or purified. The first alcohol or the second alcohol can be the alcohol obtained in step B. At this time, the alcohol obtained in step B can be appropriately purified by distillation or the like and used as a first alcohol or a second alcohol.

　一般式（４）、一般式（５）及び一般式（６）中、Ｒ’は炭素原子数１～６の直鎖状のアルキル基、又は炭素原子数３～６の分岐状のアルキル基を示す。なお、一般式（４）及び一般式（５）のペンテン酸エステルは、シス体とトランス体の一方又は両方を含んでもよい。 (Step C)
In step C, as shown in the following reaction formula (III), γ-valerolactone (a compound represented by the general formula (3)) obtained in step B and a second alcohol (R′OH) The reaction is carried out in the presence of an acid catalyst or a base catalyst to obtain a pentenoate ester. The pentenoic acid ester may contain at least one selected from the group consisting of general formula (4), general formula (5) and general formula (6).

In the general formulas (4), (5) and (6), R ′ represents a linear alkyl group having 1 to 6 carbon atoms, or a branched alkyl group having 3 to 6 carbon atoms. Show. The pentenoic acid ester of the general formula (4) and the general formula (5) may contain one or both of a cis form and a trans form.

In step C, the γ-valerolactone obtained in step B is used. As γ-valerolactone, one produced in step B can be used without particular purification, or one purified by distillation or the like may be used.

The second alcohol (R'OH) used in step C may be, for example, the alcohol exemplified for the first alcohol. The second alcohol preferably comprises at least one selected from the group consisting of methanol, ethanol, 1-propanol and 1-butanol, and more preferably comprises methanol.

The second alcohol used in step C and the first alcohol used in step A may be the same or different.

As the catalyst (acid catalyst or base catalyst) used in step C, acid catalysts such as p-toluenesulfonic acid, trifluoromethanesulfonic acid, silica-alumina, beta zeolite, X-type zeolite or the like, or Group 1 of the periodic table Base catalysts such as oxides, carbonates and silicates of metals, group 2 metals and rare earth metals can be mentioned. Preferably, the catalyst used in step C comprises zeolite X. The catalyst may be composed of only X-type zeolite, or may be one in which a metal component is supported on the support with X-type zeolite as a support. When the catalyst used in the step C contains zeolite X, by-production of ether can be suppressed, and the selectivity to the second alcohol-based pentenoate can be improved. In addition, the conversion of γ-valerolactone can be increased. These factors make it possible to obtain a pentenoate ester in a high yield without a large excess of the second alcohol.

The intrapore cation of the zeolite X is not particularly limited. From the viewpoint of increasing the yield of pentenoate ester, the intrapore cation preferably contains at least one of a proton and a sodium cation. From the viewpoint of increasing both the yield and selectivity of the pentenoate ester, the intrapore cation more preferably contains a sodium cation.

The reaction of step C may be a liquid phase reaction (reactive distillation method) or may be a gas phase reaction.

When the reaction of step C is carried out in a liquid phase (reactive distillation mode), for example, the catalyst, γ-valerolactone and the second alcohol are mixed in a reactor and reacted while being stirred. The pentenate ester to be synthesized is continuously withdrawn by distillation together with the second alcohol. In parallel to this, a second alcohol is continuously fed to the reactor in the same amount as the amount of the second alcohol withdrawn.

When the reaction of step C is carried out in the gas phase, for example, the reaction is carried out while flowing a mixture of γ-valerolactone and a second alcohol in a reaction tube filled with a catalyst. In addition, you may distribute | circulate an inert gas as carrier gas as needed. Also, an inert solid charge may be placed in the reaction tube to support the catalyst bed loaded in the reaction tube. Furthermore, in order to maintain the temperature of the catalyst bed in the reaction tube within a predetermined range, a bed of inert solid packing may be provided on the catalyst bed as a preheating bed.

The reaction temperature for carrying out the reaction of step C is preferably 180 to 280 ° C., more preferably 200 to 250 ° C. The reaction pressure for carrying out the reaction of step C is preferably atmospheric pressure to 5 MPa, and more preferably atmospheric pressure to 2 MPa. The reaction temperature and reaction pressure may be changed intermittently or continuously within the above range.

The amount of the second alcohol used is preferably 1 to 20 moles (1 to 20 mole equivalents), more preferably 2 to 10 moles (2 to 10 moles) per mole of γ-valerolactone used. Equivalent). By setting the amount of the second alcohol used in such a range, it is possible to obtain the pentenoic acid ester, which is the object of Step C, in a high yield.

In the step C, a solvent different from the alcohol may be used from the viewpoint of easiness of supply of the raw material, improvement of stirring property in liquid phase reaction, or improvement of flowability in gas phase reaction, etc. . The solvent is not particularly limited as long as it does not significantly inhibit the reaction.

As the solvent, for example, hydrocarbons such as heptane, hexane, cyclohexane and toluene; Amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone; diethyl ether, Ethers such as diisopropyl ether, 1,2-dimethoxyethane, 1,2-diethoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, tetrahydrofuran, and dioxane; and halogenated hydrocarbons such as methylene chloride, dichloroethane, and chlorocyclohexane Can be mentioned. Among these, preferred solvents include hydrocarbons and ethers, and more preferred solvents include ethers. In addition, the above-mentioned solvent may be used individually by 1 type, and may be used combining 2 or more types.

The amount of the solvent used is preferably 0 to 50 parts by mass, more preferably 0 to 25 parts by mass, with respect to 1 part by mass of the raw material (total of γ-valerolactone and second alcohol) used in step C. It is. By setting the amount of the solvent used in such a range, stirring and circulation can be rapidly performed, and the reaction can be smoothly progressed.

The conversion of γ-valerolactone in step C is preferably 85% or more, more preferably 90% or more. The conversion of the alcohol in step C is preferably 10% or more, more preferably 12% or more. The conversion of γ-valerolactone and alcohol in the present disclosure is on a molar basis.

The selectivity of pentenoic acid ester in step C is preferably 85% or more, more preferably 90% or more based on γ-valerolactone, and preferably 85% or more, more preferably 90% or more based on alcohol. It is above. The selectivity of pentenoate in the present disclosure is on a molar basis based on γ-valerolactone.

The yield of pentenoic acid ester in step C is preferably 85% or more, more preferably 90% or more. The yield of pentenoate in the present disclosure is on a molar basis based on γ-valerolactone.

The pentenoic acid ester should just contain at least 1 type chosen from General formula (4), General formula (5), and General formula (6), The ratio is not specifically limited. The yield of 2-pentenoic acid ester represented by the general formula (4) is, for example, 10 to 60%. The yield of 3-pentenoic acid ester represented by the general formula (5) is, for example, 35 to 50%. The yield of 4-pentenoic acid ester represented by the general formula (6) is, for example, 2 to 15%.

After completion of step C, the obtained reaction liquid is subjected to general operations (purification step) such as filtration, concentration, extraction, distillation, sublimation, recrystallization, column chromatography, etc. May be isolated or purified.

As one embodiment of the present invention, a pentenoic acid ester having a biomass degree determined by accelerator mass spectrometry of 40% or more is provided. Here, the degree of biomass is calculated by accelerator mass spectrometry in accordance with ASTM D6866-10 standard, and indicates the degree to which the carbon skeleton of the pentenoate ester is derived from the biomass material.

The biomass degree of the pentenoate ester determined by accelerator mass spectrometry may be 45% or more, 50% or more, 55% or more, 60% or more, 70% or more, or 80% or more, 95% or less, 90% Or less or 85% or less. The degree of biomass determined by accelerator mass spectrometry of pentenoate may be 40 to 100%.

[Method for producing adipic acid compound]
The method for producing a pentenoic acid ester derivative may further include the following step D in addition to the above steps A to C. In this case, the adipic acid compound can be obtained by the production method. The adipic acid compound is adipic acid or an ester thereof. The adipic acid ester may be adipic acid diester or adipic acid monoester.

(Step D)
Step D is a step of reacting the pentenoic acid ester obtained in Step C with a formic acid ester in the presence of a complex metal to obtain an adipic acid compound.

　一般式（２）及び一般式（４）～（７）において、Ｒ及びＲ’は炭素原子数１～６の直鎖状のアルキル基、又は炭素原子数３～６の分岐状のアルキル基を示す。なお、一般式（２）及び一般式（４）～（７）において、Ｒ及びＲ’は、通常、同一であるが、異なっていてもよい。また、一般式（４）及び一般式（５）のペンテン酸エステルは、シス体とトランス体の一方又は両方を含んでもよい。 In the step D, as shown in the following reaction formula (IV), the pentenoic acid ester obtained in the step C (compounds represented by the general formula (4), the general formula (5) and the general formula (6)), and a formic acid ester Are reacted in the presence of a complex metal to obtain an adipic acid diester as an adipic acid compound. The adipic acid diester is a compound represented by the general formula (7).

In the general formulas (2) and (4) to (7), R and R ′ each represent a linear alkyl group having 1 to 6 carbon atoms, or a branched alkyl group having 3 to 6 carbon atoms. Show. In general formulas (2) and (4) to (7), R and R ′ are usually the same, but may be different. The pentenoic acid ester of the general formula (4) and the general formula (5) may contain one or both of a cis form and a trans form.

In step D, the pentenoic acid ester obtained in step C is used. The pentenoic acid ester obtained in Step C may be used as it is without particular purification, or one purified by distillation or the like may be used.

The formate ester used in step D may be one obtained in step A. At this time, it is preferable that the formate obtained in Step A be appropriately purified by distillation or the like.

The amount of the formic acid ester used is preferably 1 to 20 moles (1 to 20 molar equivalents), more preferably 2 to 10 moles (2 to 10 molar equivalents) per 1 mole of pentenic acid ester. .

In the step D, a solvent may be used to improve the stirring property and the like. Such solvent is not particularly limited as long as it does not significantly inhibit the reaction, and examples thereof include methanol, ethanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, tert-butyl alcohol, and ethylene glycol Alcohols such as heptane; hydrocarbons such as heptane, hexane, cyclohexane and toluene; Amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone; diethyl ether, diisopropyl Ethers such as ether, 1,2-dimethoxyethane, 1,2-diethoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, tetrahydrofuran, and dioxane; and methylene chloride, diethylene glycol Roroetan, and halogenated hydrocarbons such as chloro cyclohexane. Among these, preferably, at least one selected from the group consisting of alcohols and ethers is used, and more preferably alcohols are used. One of these solvents may be used alone, or two or more thereof may be used in combination.

The amount of the solvent used in step D is preferably 0 to 100 parts by mass, more preferably 0 to 50 parts by mass, with respect to 1 part by mass of the pentenoic acid ester.

The complex metal used in step D is a metal compound containing at least one selected from metal elements belonging to Groups 8 to 10 of the periodic table (Group 8 to 10 metal elements), a ligand, and a protonic acid , Formed from.

As Group 8 to 10 metal elements, iron (Fe), ruthenium (Ru), cobalt (Co), rhodium (Rh), iridium (Ir), nickel (Ni), palladium (Pd), and platinum (Pt) Etc. The Group 8-10 metal element is preferably palladium (Pd). The metal compound contained in the complex metal is preferably a compound (palladium compound) containing palladium as a metal element.

Specific examples of the palladium compound include, for example, palladium sulfates such as palladium sulfate; palladium nitrates such as palladium nitrate; palladium carbonates such as palladium carbonate; palladium polyoxo such as palladium heteropolyacid and palladium isopolyacid Anion salts; Various palladium inorganic acid salts such as palladium halides such as palladium chloride, palladium bromide and palladium iodide; Palladium organic acid salts such as palladium acetate; Ammine complexes of palladium hydroxide, palladium oxide and the above various compounds, Organic and inorganic complexes such as amine complexes, halogeno complexes (including, for example, tetrachloro palladium acid, sodium and potassium salts thereof), cyano complexes, organic palladium compounds and the like can be mentioned. Among these, the palladium compound preferably contains at least one selected from the group consisting of palladium acetate and palladium chloride, and more preferably palladium acetate.

The above metal compounds may be used alone or in combination of two or more. The two or more metal compounds may be a mixture or a complex compound.

The amount of the metal compound (eg, palladium compound) used is preferably 0.005 to 0.1 mol (0.005 to 0.1 molar equivalent), and more preferably 1 mol of pentenoic acid ester. It is 0.01 to 0.05 mole (0.01 to 0.05 mole equivalent).

The ligand contained in the complex metal is not particularly limited, but a phosphine ligand is preferably used. Examples of phosphine ligands include triphenylphosphine, tri (4-methylphenyl) phosphine, tri (3,5-dimethylphenyl) phosphine, tri (2,4,6-trimethylphenyl) phosphine, tri (4- Methoxyphenyl) phosphine, tri (3,5-dimethoxyphenyl) phosphine, methyl diphenyl phosphine, ethyl diphenyl phosphine, dimethyl phenyl phosphine, diethyl phenyl phosphine, trimethyl phosphine, triethyl phosphine, tricyclohexyl phosphine, diphenyl phosphino methane, diphenyl phos Finoethane, diphenylphosphinopropane, 1,1′-diphenylphosphinoferrocene, 1,2-bis (diphenylphosphinomethyl) benzene, and 1,2-bis (di-t rt- butylphosphinomethyl) benzene, bis [2- (diphenylphosphino) phenyl] ether, 4,5-bis (diphenylphosphino) -9,9-dimethylxanthene and the like. The ligand preferably comprises at least one member selected from the group consisting of 1,2-bis (diphenylphosphinomethyl) benzene and 1,2-bis (di-tert-butylphosphinomethyl) benzene, Preferably, 1,2-bis (di-tert-butylphosphinomethyl) benzene is included.

The amount of the ligand used is preferably 2 to 20 moles (2 to 20 mole equivalents), more preferably 4 to 10 moles (4 to 10 mole equivalents) per mole of the metal compound (eg, palladium compound) ).

The protonic acid contained in the complex metal is not particularly limited, and examples thereof include sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, p-toluenesulfonic acid and the like. The protic acid preferably comprises p-toluenesulfonic acid.

The amount of protonic acid used is preferably 2 to 20 moles (2 to 20 mole equivalents), more preferably 4 to 10 moles (4 to 10 moles) per mole of metal compound (eg, palladium compound). Equivalent).

The reaction temperature for carrying out the reaction of step D is preferably 50 to 200 ° C., more preferably 80 to 150 ° C.

Step D may be performed under an inert gas atmosphere such as nitrogen or argon, or under a carbon monoxide gas atmosphere. The reaction pressure for carrying out the reaction of step D is preferably atmospheric pressure to 5 MPa, and more preferably atmospheric pressure to 2 MPa. The reaction temperature and reaction pressure may be changed intermittently or continuously within the above range.

In this embodiment, in step D, a reaction liquid containing the target adipic acid ester can be obtained.

The conversion of the pentenoic acid ester in step D is preferably 30% or more, more preferably 35% or more. The conversion of pentenoate in the present disclosure is on a molar basis.

The yield of the adipic acid diester in step D is preferably 30% or more, more preferably 35% or more. The yield of adipic acid diester in the present disclosure is a molar yield based on pentenoic acid ester.

After completion of the above step D, the obtained reaction solution is subjected to general operations (purification step) such as filtration, concentration, extraction, distillation, sublimation, recrystallization, column chromatography, etc. The acid ester may be isolated or purified.

The present embodiment may, as a variant, further include the following step E in which the adipic acid compound obtained in step D is hydrolyzed in addition to the above steps A to D. In this modification, adipic acid or adipic acid monoester can be produced as the adipic acid compound.

　一般式（７）において、Ｒ及びＲ’は炭素原子数１～６の直鎖状のアルキル基、又は炭素原子数３～６の分岐状のアルキル基を示す。なお、一般式（７）において、Ｒ及びＲ’は、通常、同一であるが、異なっていてもよい。また、一般式（８）において、Ｒ’’は、水素原子、又は一般式（７）におけるＲ若しくはＲ’と同義である。 (Step E)
In step E, as shown in the following reaction formula (V), the adipic acid diester obtained in step D is hydrolyzed to obtain adipic acid or adipic acid monoester (compound represented by formula (8)).

In the general formula (7), R and R ′ each represent a linear alkyl group having 1 to 6 carbon atoms or a branched alkyl group having 3 to 6 carbon atoms. In general formula (7), R and R ′ are usually the same, but may be different. In addition, in the general formula (8), R ′ ′ has the same meaning as a hydrogen atom or R or R ′ in the general formula (7).

The hydrolysis of the adipic acid diester can be carried out with either an acid or a base. Examples of the acid include hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid and the like. Moreover, as a base, ammonia, sodium hydroxide, potassium hydroxide etc. are mentioned, for example.

The yield of adipic acid in step E is preferably 90% or more, more preferably 95% or more. The yield of adipic acid in the present disclosure is on a molar basis based on the adipic acid diester.

As described above, according to the method for producing a pentenoic acid ester derivative according to the present embodiment and the modification thereof, at least one selected from the group consisting of adipic acid diester, adipic acid monoester, and adipic acid from biomass raw materials The adipic acid compound containing can be manufactured efficiently.

[Method for producing 1,6-hexanediol]
The process for producing a pentenoic acid ester derivative may further include a process F in addition to the processes A to D or the processes A to E described above. In this case, 1,6-hexanediol can be obtained by the production method.

(Step F)
Step F is a step of reacting the adipic acid compound with a hydrogen source to obtain 1,6-hexanediol. The adipic acid compound in step F may be the adipic acid diester obtained in step D, or the adipic acid or adipic acid monoester obtained in step E. Among these, the adipic acid diester obtained in Step D is preferable from the viewpoint of the life of the hydrogenation catalyst described later.

In step F, the adipic acid compound (the compound represented by the above general formula (7) or (8)) and a hydrogen source are reacted to obtain 1,6-hexanediol.

The hydrogen source used in step F is not particularly limited. Specifically, for example, hydrogen gas, alcohol, formic acid, hydrazine, sodium borohydride, lithium aluminum hydride and the like can be mentioned. The hydrogen source is preferably hydrogen gas from the viewpoint of easy separation and purification after completion of the reaction.

In step F, the adipic acid compound and the hydrogen source may be reacted in the presence of a hydrogenation catalyst. The hydrogenation (hydrogenation) catalyst used in step F is a catalyst containing a metal element, and any catalyst capable of hydrogenating (hydrogenation) a carbonyl compound such as an ester and a carboxyl group can be selected. . The hydrogenation catalyst preferably contains one kind of metal element such as nickel (Ni), copper (Cu), ruthenium (Ru), rhodium (Rh), palladium (Pd), iridium (Ir), platinum (Pt), etc. Or it is a solid catalyst containing 2 or more types, More preferably, it is a solid catalyst containing copper (Cu).

The total content of the above-mentioned metal elements in the hydrogenation (hydrogenation) catalyst is preferably 1% by mass to 80% by mass, and more preferably 5% by mass to 60%, based on the total mass of the hydrogenation catalyst. It is less than mass%. The metal element contained in the hydrogenation catalyst may be present as a zero-valent metal or metal oxide. When the ratio of metal oxides is high, reduction treatment may be performed in advance with hydrogen gas or the like before the reaction, or may be used for the reaction as it is.

The hydrogenation catalyst may contain a carrier. The carrier may be, for example, those exemplified in Step B.

The said hydrogenation catalyst may contain the other metallic element other than the metallic element mentioned above. Other metallic elements may be present as zero-valent metals or metal oxides. Examples of other metal elements include chromium (Cr), manganese (Mn), rhenium (Re), zinc (Zn), magnesium (Mg), sodium (Na), calcium (Ca) and the like.

In the reaction of step F, either a batch system (batch system) or a continuous system can be selected. In addition, depending on the nature of the hydrogenation catalyst, it can be carried out in both homogeneous and heterogeneous (suspension reaction) reaction systems.

When the reaction of step F is carried out batchwise, for example, a hydrogenation catalyst and an adipic acid compound are mixed and reacted under stirring in a hydrogen atmosphere.

When the reaction of step F is carried out continuously, for example, the reaction is conducted while hydrogen and an adipic acid compound are caused to flow in a reaction tube filled with a hydrogenation catalyst. In addition, if necessary, an inert solid charge that supports the charge of the catalyst in the reaction tube may be disposed in the reaction tube.

The reaction temperature for carrying out the reaction of step F may preferably be 50 to 250 ° C., and may be 150 to 220 ° C. The reaction pressure for carrying out the reaction of step F may be a hydrogen partial pressure of normal pressure to 10 MPa.

The reaction temperature and reaction pressure may be changed intermittently or continuously within the relevant range. By setting the reaction temperature and the reaction pressure in the above ranges, it is possible to obtain 1,6-hexanediol at high yield and high selectivity at high reaction rate while suppressing the formation of by-products.

In the reaction of step F, a solvent may be used for the ease of supply of the adipic acid compound as the raw material and the improvement of the stirring property in the batch system, or the improvement of the flowability in the continuous system, etc. . The solvent used in step F may be, for example, the solvent exemplified as the solvent used in step B.

The amount of the solvent used in step F is preferably 0 to 100 parts by mass, more preferably 0 to 50 parts by mass, with respect to 1 part by mass of the adipic acid compound. By setting the amount of solvent used in this range, stirring or circulation can be rapidly performed, and the reaction can be smoothly progressed.

The conversion of the adipic acid compound in step F is preferably 80% or more, more preferably 90% or more, and still more preferably 95% or more. The conversion of the adipic acid compound in step F is on a molar basis.

The yield of 1,6-hexanediol in step F is preferably 80% or more, more preferably 85% or more. The yield of 1,6-hexanediol in the present disclosure is the yield on a molar basis based on 1,6-hexanediol.

In the present embodiment, in step F, a reaction liquid containing 1,6-hexanediol can be obtained. After completion of the above step F, the obtained reaction liquid is subjected to general operations (purification step) such as filtration, concentration, extraction, distillation, sublimation, recrystallization, column chromatography, etc. 6-hexanediol may be isolated or purified.

[Method of producing 1,3-butadiene]
The method for producing a pentenoic acid ester derivative may further include the following step G in addition to the above steps A to C. In this case, 1,3-butadiene can be obtained by the production method.

(Step G)
Step G is a step of reacting the pentenoic acid ester obtained in step C, water and an acid anhydride in the presence of a complex metal to obtain 1,3-butadiene.

In step G, the pentenoic acid ester obtained in step C is used. The pentenoic acid ester obtained in Step C may be used as it is without particular purification, or one purified by distillation or the like may be used.

The amount of water used may be 1 to 10 moles (1 to 10 mole equivalent), 1.2 to 5.0 moles (1.2 to 5.0 mole equivalent) per 1 mole of pentenate ester. And 1.5 moles to 2.5 moles (1.5 to 2.5 mole equivalents).

Examples of the acid anhydride include acetic anhydride, succinic anhydride, phthalic anhydride, maleic anhydride, benzoic anhydride and the like. The amount of the acid anhydride used may be 1 to 10 moles (1 to 10 mole equivalents) and 1.2 to 5 moles (1.2 to 5 mole equivalents) per mole of pentenoic acid ester. And may be 1.5 to 2.5 moles (1.5 to 2.5 molar equivalents).

In the step G, a solvent may be used to improve the stirring property and the like. The solvent used in step G may be the solvent exemplified as the solvent used in step B.

The amount of the solvent used in step G is preferably 0 to 100 parts by mass, more preferably 0 to 50 parts by mass, with respect to 1 part by mass of the pentenoic acid ester.

The complex metal used in step D is formed of a metal compound containing at least one selected from metal elements belonging to Groups 8 to 10 of the Periodic Table (Group 8 to 10 metal elements), and a ligand Ru.

As Group 8 to 10 metal elements, iron (Fe), ruthenium (Ru), cobalt (Co), rhodium (Rh), iridium (Ir), nickel (Ni), palladium (Pd), and platinum (Pt) Etc. The Group 8-10 metal element is preferably palladium (Pd). The metal compound contained in the complex metal is preferably a compound (palladium compound) containing palladium as a metal element.

Examples of palladium compounds include those exemplified above. The palladium compound preferably contains at least one selected from the group consisting of palladium acetate and palladium chloride, and more preferably palladium chloride.

The above metal compounds may be used alone or in combination of two or more. The two or more metal compounds may be a mixture or a complex compound.

The amount of the metal compound (eg, palladium compound) used may be 0.005 to 0.5 mol (0.005 to 0.5 molar equivalent), relative to 1 mol of pentenate ester, 0.01 It may be up to 0.3 mole (0.01 to 0.3 mole equivalent).

The ligand contained in the complex metal is not particularly limited, but a phosphine ligand is preferably used. As the phosphine ligand, for example, those exemplified above can be used, and preferably bis [2- (diphenylphosphino) phenyl] ether is used.

The amount of the ligand used may be 1 to 50 moles (1 to 50 mole equivalent), 1 to 10 moles (1 to 10 mole equivalent) per 1 mole of the metal compound (for example, palladium compound) It may be.

The reaction temperature for carrying out the reaction of step G may be 50 to 250 ° C., and may be 80 to 200 ° C.

Step G may be performed under an inert gas atmosphere such as nitrogen or argon, or under a carbon monoxide gas atmosphere. The reaction pressure at the time of carrying out the reaction of step G may be normal pressure to 5 MPa, and may be normal pressure to 2 MPa. The reaction temperature and reaction pressure may be changed intermittently or continuously within the above range.

In this embodiment, in step G, a reaction liquid or product gas containing 1,3-butadiene can be obtained.

The conversion of the pentenoic acid ester in step G is preferably 80% or more, more preferably 90% or more, and still more preferably 95% or more. The conversion of pentenoate in step G is on a molar basis.

The yield of 1,3-butadiene in step G is preferably 80% or more, more preferably 90% or more. The yield of 1,3-butadiene in step G is a yield on a molar basis based on the pentenoate ester.

As another form of step G, a step of reacting pentenoic acid ester with water in the presence of an acid catalyst to obtain butene (a mixture of 1-butene and 2-butene), and butene in the presence of a metal oxide catalyst The method further includes the step of dehydrogenating under to obtain 1,3-butadiene.

(Step of reacting pentenoic acid ester with water in the presence of a catalyst to obtain butene (a mixture of 1-butene and 2-butene))
The amount of water used in this step may be 1 to 100 mol (1 to 100 mol equivalent), or 5.0 to 60 mol (5.0 to 60 mol equivalent) per 1 mol of pentenate ester. It may be 10 to 30 moles (10 to 30 mole equivalents).

As the acid catalyst in this step, homogeneous acids such as sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid, and solid acids such as silica-alumina, zeolite, niobic acid, sulfonated titania, sulfonated zirconia, sulfonated activated carbon and the like are used. The acid catalyst is preferably silica-alumina.

In the reaction of this step, for example, a mixture of a pentenoate and water is allowed to flow in a reaction tube filled with a solid acid catalyst. In addition, if necessary, an inert solid charge that supports the charge of the catalyst in the reaction tube may be disposed in the reaction tube.

The reaction in this step is carried out under an inert gas atmosphere such as nitrogen or argon. The reaction temperature at this time may preferably be 300 to 500 ° C., and may be 350 to 450 ° C. The reaction pressure may be normal pressure to 5 MPa, and may be normal pressure to 2 MPa. The reaction temperature and reaction pressure may be changed intermittently or continuously within the above range.

In this embodiment, a product gas containing butene (a mixture of 1-butene and 2-butene) can be obtained.

(Step of dehydrogenating butene (a mixture of 1-butene and 2-butene) to obtain 1,3-butadiene)
In the reaction of this step, for example, butene (a mixture of 1-butene and 2-butene) is allowed to react while flowing through a reaction tube filled with a metal oxide catalyst. In addition, if necessary, an inert solid charge that supports the charge of the catalyst in the reaction tube may be disposed in the reaction tube.

As the metal oxide catalyst in this step, a composite oxide containing zinc and iron, a composite oxide containing cobalt and iron, a composite oxide containing nickel and iron, a composite oxide containing copper and iron, bismuth and molybdenum Complex oxides, etc. are used.

The reaction in this step is carried out under an inert gas atmosphere such as nitrogen or argon. The reaction temperature at this time may preferably be 350 to 500 ° C., and may be 400 to 450 ° C. The reaction pressure may be normal pressure to 5 MPa, and may be normal pressure to 2 MPa. The reaction temperature and reaction pressure may be changed intermittently or continuously within the above range.

In the present embodiment, a product gas containing 1,3-butadiene can be obtained.

[Method for producing ε-caprolactam]
The method for producing a pentenoic acid ester derivative may further include the following steps H to I in addition to the above steps A to C. In this case, ε-caprolactam can be obtained by the production method.

(Step H)
Step H is a step of reacting the pentenoic acid ester obtained in Step C, carbon monoxide and hydrogen in the presence of a complex metal to obtain 5-formylpentanoic acid ester (also referred to as 5-formylvalerate). .

　一般式（４）～（６）及び（９）において、Ｒ’は炭素原子数１～６の直鎖状のアルキル基、又は炭素原子数３～６の分岐状のアルキル基を示す。なお、一般式（４）～（６）及び（９）において、Ｒ’は、通常、同一であるが、異なっていてもよい。 In step H, as shown in the following reaction formula (VI), the pentenoic acid ester obtained in step C (general formula (4), compounds represented by general formula (5) and general formula (6)) and carbon monoxide Is reacted with hydrogen in the presence of a complex metal to give 5-formylpentanoic acid ester. 5-formylpentanoic acid ester is a compound represented by the general formula (9).

In the general formulas (4) to (6) and (9), R ′ represents a linear alkyl group having 1 to 6 carbon atoms or a branched alkyl group having 3 to 6 carbon atoms. In general formulas (4) to (6) and (9), R ′ is usually the same, but may be different.

In step H, the pentenoic acid ester obtained in step C is used. The pentenoic acid ester obtained in Step C may be used as it is without particular purification, or one purified by distillation or the like may be used.

As the complex metal used in step H, complex metals commonly used in hydroformylation reactions can be used. For example, the complex metal used in step H is a metal compound containing at least one selected from metal elements belonging to Groups 8 to 10 of the periodic table (Group 8 to 10 metal elements), and a ligand It is formed.

As Group 8 to 10 metal elements, iron (Fe), ruthenium (Ru), cobalt (Co), rhodium (Rh), iridium (Ir), nickel (Ni), palladium (Pd), and platinum (Pt) Etc. The Group 8 to 10 metal element is rhodium (Rh). The metal compound contained in the complex metal is preferably a compound containing rhodium as a metal element.

As a compound containing rhodium, for example, chloro (1,5-cyclooctadiene) rhodium (I) dimer, bis (triphenylphosphine) rhodium (I) carbonyl chloride, di-μ-chlorotetracarbonyldirhodium (I) Di-μ-chlorotetraethylenedirhodium (I), (acetylacetonato) (1,5-cyclooctadiene) rhodium (I), (acetylacetonato) (norbornadiene) rhodium (I), (acetylacetonato) 2.) Dicarbonylrhodium (I), tris (triphenylphosphine) rhodium (I) chloride and the like.

The above metal compounds may be used alone or in combination of two or more. The two or more metal compounds may be a mixture or a complex compound.

The amount of the metal compound used may be 0.001 to 0.050 mol (0.001 to 0.050 molar equivalent), and 0.005 to 0.0.0.0 mol, per 1 mol of the pentenate ester. It may be molar (0.005 to 0.015 molar equivalents).

The ligand contained in the complex metal is not particularly limited, but a phosphine ligand is preferably used. As the phosphine ligand, for example, those exemplified above can be used, and from the viewpoint of high selectivity, preferably 4,5-bis (diphenylphosphino) -9,9-dimethylxanthene is used.

The amount of the ligand used may be 1 to 50 moles (1 to 50 mole equivalents) or 1 to 10 moles (1 to 10 mole equivalents) with respect to 1 mole of the metal compound.

Step H may be performed under an atmosphere of hydrogen and carbon monoxide. The molar ratio of carbon monoxide gas to hydrogen gas may be from 1/5 to 5/1, from 1/3 to 3/1, or from 1/1.

In the reaction of step H, a solvent may be used for the ease of supply of pentenoic acid ester as a raw material and the improvement of the stirring property in a batch system, or the improvement of flowability in a continuous system, etc. . The solvent used in step H may be, for example, the solvents exemplified as the solvent used in step B. The solvents may be used alone or in combination of two or more.

The amount of the solvent used in step H is preferably 0 to 100 parts by mass, more preferably 0 to 50 parts by mass, with respect to 1 part by mass of the pentenoic acid ester. By setting the amount of solvent used in this range, stirring or circulation can be rapidly performed, and the reaction can be smoothly progressed.

The reaction temperature for carrying out the reaction of step H may be 50 to 250 ° C., and may be 80 to 150 ° C.

The reaction pressure for carrying out the reaction of step H may be normal pressure to 5 MPa, and may be normal pressure to 3 MPa. The reaction temperature and reaction pressure may be changed intermittently or continuously within the above range.

In this embodiment, in step H, a reaction liquid containing 5-formylpentanoic acid ester can be obtained. After completion of step H, the solution containing 5-formylpentanoic acid ester is subjected to general operations (purification step) such as filtration, concentration, extraction, distillation, sublimation, recrystallization, column chromatography, etc. , 5-formylpentanoic acid ester may be purified.

The conversion of the pentenoic acid ester in step H is preferably 80% or more, more preferably 90% or more. The conversion of pentenoate in step H is on a molar basis.

The yield of 5-formylpentanoic acid ester in step H is preferably 15% or more, more preferably 20% or more. The yield of 5-formylpentanoic acid ester in step H is a molar yield based on pentenoic acid ester.

(Step I)
Step I is a step of reacting 5-formylpentanoic acid ester (a compound represented by the above general formula (9)), ammonia and a hydrogen source to obtain ε-caprolactam.

In step I, an aqueous ammonia solution can be used to supply ammonia. The amount of ammonia used is preferably 1 to 20 moles (1 to 20 mole equivalent), more preferably 3 to 15 moles (3 to 15 mole equivalent), per 1 mole of 5-formylpentanoic acid ester. .

Examples of the hydrogen source used in step I include hydrogen gas, alcohol, formic acid, hydrazine, sodium borohydride, lithium aluminum hydride and the like. The hydrogen source is preferably hydrogen gas from the viewpoint of easy separation and purification after completion of the reaction.

In step I, 5-formylpentanoic acid ester, ammonia and a hydrogen source may be reacted in the presence of a metal catalyst. The metal catalyst used in the process is a catalyst containing a metal element. The metal catalyst includes, for example, one or two metal elements such as nickel (Ni), copper (Cu), ruthenium (Ru), rhodium (Rh), palladium (Pd), iridium (Ir), platinum (Pt), etc. It may be a solid catalyst containing species or more, preferably a solid catalyst containing palladium (Pd).

The total content of the above-mentioned metal elements in the metal catalyst is preferably 1% by mass to 50% by mass, and more preferably 2% by mass to 30% by mass, based on the total mass of the metal catalyst. The metal element contained in the hydrogenation catalyst may be present as a zero-valent metal or metal oxide. When the ratio of metal oxides is high, reduction treatment may be performed in advance with hydrogen gas or the like before the reaction, or may be used for the reaction as it is.

The metal catalyst may contain a carrier. As the carrier, porous ones are suitably used. For example, porous silica, porous alumina, porous silica alumina (aluminosilicate), porous ceria, porous magnesia, porous calcia, porous titania, porous Silica (titanosilicate), porous zirconia, activated carbon, zeolite, mesoporous material (mesoporous-alumina, mesoporous-silica, mesoporous-carbon) and the like. The support preferably includes porous silica, porous alumina, porous activated carbon, and porous zeolite. These carriers may be used alone or in combination of two or more.

In the reaction of step I, either a batch system (batch system) or a continuous system can be selected. In addition, depending on the nature of the metal catalyst, it can be carried out in both homogeneous and heterogeneous (suspension reaction) reaction systems.

In step I, for example, a metal catalyst, 5-formylpentanoic acid ester, and ammonia may be mixed and reacted while stirring under a hydrogen atmosphere.

The reaction temperature for carrying out the reaction of step I is preferably 20 to 200 ° C., more preferably 30 to 150 ° C. Further, the reaction pressure at the time of carrying out the reaction of step I is, as a hydrogen partial pressure, normal pressure to 10 MPa, more preferably normal pressure to 5 MPa.

The reaction temperature and reaction pressure may be changed intermittently or continuously within the relevant range. By setting the reaction temperature and the reaction pressure in the above ranges, it is possible to obtain ε-caprolactam in high yield and high selectivity at a high reaction rate while suppressing the formation of by-products.

In the reaction of step I, a solvent is used to facilitate the supply of 5-formylpentanoic acid ester as a raw material and to improve the stirring property in a batch system, or to improve the flowability in a continuous system, etc. May be The solvent used in Step I may be, for example, the solvent exemplified as the solvent used in Step B. The solvents may be used alone or in combination of two or more.

The amount of the solvent used in step I is preferably 0 to 100 parts by mass, more preferably 0 to 50 parts by mass, with respect to 1 part by mass of 5-formylpentanoic acid ester. By setting the amount of solvent used in this range, stirring or circulation can be rapidly performed, and the reaction can be smoothly progressed.

The conversion of 5-formylpentanoic acid ester in step I is preferably 80% or more, more preferably 90% or more, and still more preferably 95%. The conversion of 5-formylpentanoic acid ester in step I is on a molar basis.

The yield of ε-caprolactam in step I is preferably 80% or more, more preferably 90% or more, and still more preferably 95%. The yield of ε-caprolactam in step I is on a molar basis based on 5-formylpentanoic acid ester.

In this embodiment, in step I, a reaction solution containing ε-caprolactam can be obtained. After completion of the above step I, the obtained reaction liquid is subjected to general operations (purification step) such as filtration, concentration, extraction, distillation, sublimation, recrystallization, column chromatography, etc. Caprolactam may be isolated or purified.

As mentioned above, although embodiment of this invention was described, this invention is not limited at all to the said embodiment.

Although the contents of the present invention will be described in more detail by way of examples, the present invention is not limited to the following examples.

Example 1 Production of Pentenoic Acid Ester Derivative
(Step A: Synthesis of levulinic acid ester and formate ester)
In an autoclave with an internal volume of 1.5 L, 37.5 g of softwood-derived pulp (cellulose content: 76% by mass) as a biomass material, and tris (2,4-pentanedionato) aluminum (III) as an additive (Al (acac) ) ₃ ) 0.49 g (1.5 mmol), 2.58 g (15 mmol) of p-toluenesulfonic acid as an acid catalyst, and 600 g of methanol are added, and reacted for 5 hours under conditions of 3.5 MPa and 180 ° C. under nitrogen atmosphere. I did. After the reaction, the reaction solution was cooled to room temperature (25 ° C.), and the contents were recovered and separated by filtration into a filtrate and a filtrate (hereinafter referred to as a reaction solution). As a result of analyzing the components in the reaction solution by gas chromatography, it was confirmed that methyl levulinate was produced in a yield of 67% and methyl formate in a yield of 77%.

(Step A ′: separation of levulinate and formate)
The obtained reaction liquid 570 g (content of methyl levulinate: 15.1 g, content of methyl formate: 5.4 g) is charged into a 1 L eggplant flask, heated and stirred at 85 ° C. under normal pressure conditions, and distilled. Did. As a result, a methanol solution of formic acid ester (content of formic acid ester: 6.8% by mass, content of methanol: 89% by mass, hereinafter referred to as "formic acid ester solution") was obtained as a distillate. The formic acid ester solution obtained here was used as a formic acid ester raw material for the synthesis reaction of adipic acid ester in step D described later. Next, the distillation residue (bottom residue) obtained by the above-mentioned distillation treatment is heated and stirred under normal pressure conditions at 90 to 95 ° C. to distill off methanol, and further reduced pressure conditions of 90 ° C. and 25 to 45 kPa The remaining impurities were distilled off by heating and stirring. The obtained distillation residue was further heated and stirred under reduced pressure conditions of 90 ° C. and 0.8 to 1.0 kPa to obtain 8.1 g of methyl levulinate as a distillate. It was confirmed that the purity of the obtained methyl levulinate obtained by gas chromatography is 99% by mass, and the purity by NMR is 99% by mass.

(Step B: Synthesis of γ-valerolactone)
In a reaction tube (φ 10 mm × 100 mm), 3.0 mL (Cu: 12 mmol, Zn) of 25 wt% Cu-32 wt% Zn / Al ₂ O ₃ catalyst (trade name: Cu-0891 T1 / 8, Engelhard) as a hydrogenation catalyst : 15 mmol) to be a hydrogenation catalyst layer. The hydrogenation catalyst contains 25% by mass of Cu and 32% by mass of Zn based on the total amount of the hydrogenation catalyst. On this hydrogenation catalyst layer, 2.0 mL of 2 mm-sized glass beads were packed as a preheating layer. As pretreatment, reduction treatment of the hydrogenation catalyst by hydrogen was performed. In the reduction treatment, 20 mL / min of hydrogen gas was introduced into the reaction tube filled with the hydrogenation catalyst and the preheated bed. The reaction tube was heated to 180 ° C. with a heater and held for 2 hours while supplying Thereafter, the temperature was set to 160 ° C., the hydrogen gas supply rate was 15.0 mL / min. And the flow of methyl levulinate obtained in step A into the reaction tube was started. The feed rate of methyl levulinate was 5.7 mmol / h. In order to stabilize the composition of the reaction liquid, collection of the reaction liquid discharged from the reaction pipe outlet was started one hour after the passage of methyl levulinate into the reaction pipe was started.

Methyl levulinate was passed continuously for 18 hours from the start of collection to obtain 11.0 g of collection liquid. The collected liquid was analyzed by gas chromatography. As a result, it was confirmed that the conversion of methyl levulinate was 100%, the yield of γ-valerolactone was 99.9%, and the reaction was proceeding. As the composition of the collection liquid, the content of γ-valerolactone was 92.9% by mass, and the content of methanol was 6.9% by mass. The collected liquid obtained here was used as a γ-valerolactone raw material in the synthesis of pentenoate in step C described later.

(Step C: Synthesis of Pentenoic Acid Ester)
In a reaction tube (φ 10 mm × 100 mm), 4.0 mL of sodium X-type zeolite catalyst (Molecular sieve 13X, manufactured by Wako Pure Chemical Industries, Ltd.) was filled to make a sodium X-type zeolite catalyst layer. In addition, 2.0 mL of 2 mm-sized glass beads were loaded on the sodium X-type zeolite catalyst layer as a preheating layer. In addition, the γ-valerolactone material obtained in step B (the content of γ-valerolactone: 92.9% by mass, the content of methanol: 6.9% by mass) to the γ-valerolactone content of 29.6 The mixture solution of γ-valerolactone and methanol was prepared by diluting with methanol so as to be% by mass.

In a reaction tube filled with a catalyst and a preheated bed, nitrogen gas of 10 mL / min. The reaction tube was heated to 230 ° C. with a heater while supplying Thereafter, the prepared mixed solution was supplied from the inlet of the reaction tube. The reaction pressure was atmospheric pressure. At this time, the mixed solution was supplied such that the feed rate of γ-valerolactone was 1.4 mmol / h and the feed rate of methanol was 11.0 mmol / h. In order to stabilize the composition of the reaction liquid, after passing the mixed solution for 1 hour, collection of the reaction liquid discharged from the reaction tube outlet was started.

The mixed solution was continuously passed for 35 hours from the start of collection to obtain 12.2 g of collection liquid. Analysis of the collected liquid by gas chromatography revealed that the conversion of γ-valerolactone is 97%, the yield of pentenoate is 95% (of which 4.7% of methyl 4-pentenoate, methyl 3-pentenoate The selectivity of pentenoate based on 44%, methyl 2-pentenoate (51%) and γ-valerolactone was 98%. Further, the conversion of methanol was 13%, and the selectivity of pentenoate based on methanol was 93%. The collection solution had a content of pentenoate of 33.9% by mass (of which 1.6% by mass of methyl 4-pentenoate, 14.9% by mass of methyl 3-pentenoate, 17.4% of methyl 2-pentenoate %), The content of methanol was 61.4% by mass, and the content of γ-valerolactone was 1.7% by mass. The obtained collection liquid was used as a pentenoic acid ester raw material in the synthesis of an adipic acid compound, 1,3-butadiene, ε-caprolactam, etc. described later.

Separately from this, the collection solution was purified by silica gel column chromatography (developing solvent: ethyl acetate / hexane = 1/10) to obtain a pentenoic acid ester (NMR purity: 99 mass%). The obtained pentenoate is a mixture of methyl 4-pentenoate, methyl 3-pentenoate and methyl 2-pentenoate, and the amounts thereof are 3.9% by mass, 46% by mass and 50% by mass, respectively. there were. The evaluation of the degree of biomass of the obtained pentenoate ester was evaluated by measuring the biomass carbon content by accelerator mass spectrometry. The biomass carbon content was calculated in accordance with ASTM D6866-10 standard. As a result, the biomass carbon content (biomass degree) of pentenoate was 84%. The biomass carbon content of the obtained methyl pentenoate is a value close to the theoretical biomass carbon content (83%), indicating that all carbons of the pentenoic acid skeleton excluding the alcohol-derived carbon is biomass-derived It was done. In addition, theoretical biomass content rate is biomass carbon content rate when all carbons of a pentenoic-acid frame | skeleton except the carbon derived from alcohol originate in biomass.

Example 2 Production of Adipic Acid Compound
(Step D: synthesis of dimethyl adipate)
4.15 g of pentenoate ester raw material obtained in step C (content of pentenoate ester: 1.41 g, content of methanol: 2.55 g) in an autoclave having an inner volume of 50 mL, and obtained in step A 16.4 g of a formic acid ester raw material (content of methyl formate: 1.11 g, content of methanol: 14.6 g) is charged, and 54 mg (0.24 mmol) of palladium acetate as a complex metal, 1,2-bis (di 380 mg (0.96 mmol) of -tert-butylphosphinomethyl) benzene and 230 mg (1.2 mmol) of p-toluenesulfonic acid monohydrate were added. The inside of the reaction vessel was purged with nitrogen gas, then pressurized to 0.5 MPa at room temperature, and reacted at 100 ° C. for 10 hours. After the reaction, the reaction solution was cooled down to room temperature and analyzed by gas chromatography. As a result, it was confirmed that the conversion of pentenoate was 46% and dimethyl adipate was obtained in a yield of 41%.

The obtained dimethyl adipate reaction solution was concentrated by an evaporator and then purified by silica gel column chromatography (solvent: toluene) to obtain 0.401 g of dimethyl adipate (18% isolated yield). The purity of the obtained dimethyl adipate by NMR was 99% by mass. Evaluation of the degree of biomass of purified dimethyl adipate was performed by measuring biomass carbon content by accelerator mass spectrometry. The biomass carbon content was calculated in accordance with ASTM D6866-10 standard. As a result, the biomass carbon content of dimethyl adipate was 80%. The biomass carbon content of the obtained dimethyl adipate was a value close to the theoretical biomass carbon content (75%), and it was shown that all carbons of the adipic acid skeleton were derived from biomass. The theoretical biomass content is the biomass carbon content when all carbon in the adipic acid skeleton is derived from biomass.

(Step E: Synthesis of Adipic Acid)
To 0.25 g (1.44 mmol) of purified dimethyl adipate, 3.0 g of a 5.0 M aqueous HCl solution was added, and allowed to stand for 24 hours for hydrolysis. The precipitated adipic acid was filtered off and washed with water (10.0 g). Drying under reduced pressure at 60 ° C. and 10 kPa gave 0.21 g (1.41 mmol, yield 98% based on dimethyl adipate) of adipic acid. The purity of the obtained adipic acid by NMR was 99% by mass.

Example 3 Production of 1,6-Hexanediol
In an autoclave having an internal volume of 50 mL, 0.87 g (5 mmol) of dimethyl adipate prepared in Example 2, 1.0 g of Cu-Zn catalyst (manufactured by JGC Catalysts and Chemicals, Inc., N 218), and 1,2-dimethoxyethane as a solvent Charged 6 mL. After replacing the inside of the reaction vessel with nitrogen gas, hydrogen was pressurized to 8.0 MPa at room temperature and reacted at 200 ° C. for 16 hours. After the reaction, the reaction liquid was analyzed by gas chromatography after cooling to room temperature, and it was found that the conversion of dimethyl adipate was 95% and 1,6-hexanediol was obtained in a yield of 88%. confirmed.

Example 4 Production of 1,3-Butadiene
0.70 g of a pentenoic acid ester raw material prepared in Example 1 (content of methyl pentenoate: 0.24 g, content of methanol: 0.46 g), 80 mg of water, and 5 mL of diethylene glycol diethyl ether as a solvent were charged. Further, as a catalyst, 18 mg of palladium chloride (manufactured by Wako Pure Chemical Industries, Ltd .; 0.1 mmol) and 162 mg of bis [2- (diphenylphosphino) phenyl] ether (manufactured by Tokyo Kasei Kogyo; 0.3 mmol) were added. The inside of the reaction vessel was purged with nitrogen and then stirred at 100 ° C. for 2 hours as pretreatment. Thereafter, 408 mg of acetic anhydride (manufactured by Wako Pure Chemical Industries, Ltd., 4 mmol) was added and reacted at 140 ° C. At this time, the outlet gas was passed through mesitylene to trap 1,3-butadiene generated as a gas. After reacting for 5 hours, quantitative analysis of the pentenoate ester and 1,3-butadiene in the reaction solution and 1,3-butadiene in the mesitylene trap by gas chromatography revealed that the conversion of methyl pentenoate is 98%. It was confirmed that the 1,3-butadiene yield was 93%.

<Example 5: Production of ε-caprolactam>
(Synthesis of 5-formylvalerate)
3.8 g (content of methyl pentenoate: 1.3 g, content of methanol: 2.5 g) of the pentenoate ester raw material prepared in Example 1 was concentrated by an evaporator to remove methanol. The concentrate of pentenoic acid ester raw material and 20 mL of 1,2-dimethoxyethane were charged into an autoclave having an inner volume of 50 mL. Further, 49 mg of chloro (1,5-cyclooctadiene) rhodium (I) dimer (0.1 mmol, made by Tokyo Chemical Industry Co., Ltd.) and 4,5-bis (diphenylphosphino) -9 were added to the obtained solution as a catalyst. , 9-dimethylxanthene 243 mg (manufactured by Tokyo Chemical Industry Co., Ltd., 0.42 mmol) were added. After replacing the inside of the reaction vessel with nitrogen gas, the mixed gas of carbon monoxide and hydrogen (CO / H ₂ = 1/1 (molar ratio)) is pressurized to 2.0 MPa at room temperature and reacted at 100 ° C. for 6 hours. The After the reaction, the reaction solution was cooled to room temperature and analyzed by gas chromatography. As a result, it was confirmed that the conversion of pentenoate was 92% and 5-formylvalerate was obtained in a yield of 31%.

The reaction solution is concentrated by an evaporator and then purified by silica gel column chromatography using ethyl acetate / hexane (1/2) as a developing solvent to obtain 0.360 g of methyl 5-formylpentanoate (methyl 5-formylvalerate) (isolated) Yield 25%).

(Synthesis of ε-caprolactam)
In an autoclave with an inner volume of 50 mL, 0.360 g (2.5 mmol) of methyl 5-formylvalerate obtained and 1.36 g of 25% ammonia water (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., 20 mmol as NH ₃ ), 1, 1 10 mL of 2-dimethoxyethane was charged, and 150 mg of 5 wt% Pd / Al ₂ O ₃ (manufactured by EN Chemcat) was further added as a catalyst. After replacing the inside of the reaction vessel with nitrogen gas, hydrogen was pressurized to 2.0 MPa at room temperature. After reacting for 2 hours at 40 ° C. first, the temperature was raised to 100 ° C., and the reaction was further performed for 4 hours. After the reaction, the reaction solution was cooled down to room temperature and analyzed by gas chromatography. As a result, the conversion of methyl 5-formylpentanoate (methyl 5-formylvalerate) was 98%, and the yield of ε-caprolactam was 86 It confirmed that it obtained by%.

Claims (14)

A method for producing a pentenoic acid ester derivative using a biomass material,
Reacting the biomass feedstock with a first alcohol in the presence of an acid catalyst to obtain levulinic acid ester and formate ester;
Step B of reacting levulinate with hydrogen source to obtain γ-valerolactone and reacting the γ-valerolactone with a second alcohol in the presence of an acid catalyst or a base catalyst to obtain a pentenoate ester A manufacturing method comprising step C. The method of claim 1, wherein the first alcohol comprises methanol. The method according to claim 1, wherein the hydrogen source comprises hydrogen gas. The method according to any one of claims 1 to 3, wherein the second alcohol comprises methanol. The method according to any one of claims 1 to 4, further comprising the step D of reacting the pentenoic acid ester with a formic acid ester in the presence of a complex metal to obtain an adipic acid compound. The method according to claim 5, wherein the formic acid ester comprises the formic acid ester obtained in the step A. The manufacturing method according to claim 5 or 6, further comprising a step E of hydrolyzing the adipic acid compound. The production method according to any one of claims 5 to 7, further comprising a step F of reacting the adipic acid compound with a hydrogen source to obtain 1,6-hexanediol. The method according to any one of claims 1 to 4, further comprising a step G of reacting the pentenoic acid ester, water and an acid anhydride in the presence of a complex metal to obtain 1,3-butadiene. The method further comprises the steps of reacting the pentenoic acid ester with water in the presence of an acid catalyst to obtain butene, dehydrogenating the butene in the presence of a metal oxide catalyst to obtain 1,3-butadiene. The production method according to any one of 1 to 4. Step H of reacting the pentenoate ester with carbon monoxide and hydrogen in the presence of a complex metal to obtain 5-formylpentanoic acid ester and reacting the 5-formylpentanoic acid ester with ammonia and a hydrogen source ε The method according to any one of claims 1 to 4, further comprising a step I of obtaining caprolactam. The biomass material is wood, sawdust, wood flour, bark, paper, pulp, paper waste, bagasse, rice husk, coconut husk, rice husk, rice bran, soybean meal, soybean meal, rapeseed meal, coffee meal, tea meal, okara, 12. The method according to any one of claims 1 to 11, comprising at least one selected from the group consisting of corn cob, corn stover, coconut hair, switch grass, alfalfa, bamboo, grass, hay, seaweed and seaweed. Production method. The method according to any one of claims 1 to 12, wherein the first alcohol or the second alcohol is an alcohol obtained in the step B. A pentenate ester having a biomass degree of 40% or more determined by accelerator mass spectrometry.